INVESTIGATION  OF  BROMONITROCAMPHANE 


BV 

PAUL  MEADE  GINNINGS 

B.  S.  University  of  Illinois,  1919 
M.  S.  University  of  Illinois,  1920 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE  UNIVERSITY 
OF  ILLINOIS,  1922. 


URBANA,  ILLINOIS 


I 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


.May:_'L8^ 


.192^ 


I HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 


SUPERVISION  BY P^l  ^ U&eul&^ i tin lug-a- 


ENTITLED  _ e ati 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


THE  DEGREE  OF Do  cto3i-Qf  - PhJLLoa-gph.y- stxy 






/ In  Charge  of  1 hesis 


l\T.  ^ ^ /\T 


cad  of  Department 


Recommendation  concurred  in* 


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AGKIT0\7LEDGMENT. 

The  author  wishes  to  take  this  opportunity  to  express 
his  indebtedness  to  Prof.  U.  A.  Noyes,  upon  whose  sugges- 
tion this  inve stigati on  was  undertaken,  and  under  whose 
kind  direction  it  was  carried  out. 


i 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/investigationofbOOginn 


TABLE  OF  CONTENTS. 

Pag  © 

I-  INTRODUCTION^-; 1 

II-  HISTORICAL  1 

III-  THEORETICAL 7 

1-  Oxidation  of  broaoni trocamphane  with  nitric  acid  7 

2-  Mechanism  of  action  of  potassium  hypobromite  on 

c ampho roxime . 8 

Oxidation  of  inf ra-campholeneni trile . 15 

4-  Action  of  dehydrating  agents  on  bromoni trocamphane  l4 

5“  Structure  of  the  two  isomeric  anhydrides.  14 

aw  Action  of  the  Grignard  reagent  on  the  first  form 

of  the  bromonitro camphane  anhydride.  17 

b-  Action  of  hydroxylamine  on  the  second  isomer  of 

bromonitro camphane  anhydride.  17 

6-  Action  of  alcoholic  sodium  hydroxide  on  the  compound 

prepared  in  18 

IV- EXPERIMENTAL. 20 

1-  Preparation  of  campho roxime . 20 

2-  Preparation  of  bromonitrocamphane . 20 

5~  Oxidation  of  bromoni trocamphane  with  dilute  nitric 

acid.  22 

4-  Oxidation  of  bromonitrocamphane  to  camphor.  24 

5-  Investigation  of  the  so-called  "hydrate"  compound.  25 

6-  Attempt  to  prepare  the  bromonitroso  compound  by  the 

action  of  bromine  on  the  camphoroxime  in  glacial 
acetic  acid  and  sodium  acetate.  26 


TABLE  OP  CONTENTS  -2. 

7-  Atteapt  to  synthesize  bromoni tro caaphane  by  the  action 

of  bromine  on  campho roxirte  in  pyridine  solution.  27 

8-  Attempt  to  prepare  the  bromonitrosocamphane.  27 

9-  Quantitative  observations  on  the  course  of  the  action 

of  potassium  hypobromite  on  camphoroxime . 29 

10-  Preparation  of  the  hydroxy-nitrosocamphane  by  the 

action  of  potassium  permanganate  on  camphoroxime.  ^0 

11-  Action  of  potassium  ferricyanide  on  camphoroxime  in 

alkaline  solution.  51 

12-  Control  of  reaction  with  potassium  hypobromite  to 

produce  the  hydroxy-ni trosocamphane  as  the  main 
product.  5^ 

Oxidation  of  inf ra-campholenenitrile  by  the  action 

of  potassium  permanganate , 5^ 

14-  Preparation  of  bromoni tro camphane  anhydride.  5^ 

15“  Attempt  to  prepare  the  organo-magnesium  compounds 
of  the  bromonitrocamphane  and  also  the  bromonitro- 
camphane  anhydride.  5^ 

16-  Action  of  the  Grignard  reagent  on  the  bromonitro- 
camphane anhydride.  Methyl  magnesium  iodide  being  used  ^6 

17-  Action  of  alcoholic  sodium  hydroxide  on  the  compound 

produced  by  the  Grignard  reaction  (see  16).  5S 

V-  SUMMARY.  40 

VI-  BIBLIOGRAPHY 4l 

VII-  VITA.  42 


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CHARTS. 


page 

I-  General  chart  of  the  cocipounds  related  to  bromonitro- 

camphane.  (Historical  Section)  2a 

II-  Chart  of  the  mechanism  of  the  reaction,  camphor oxime 

to  bromonitrocamphane.  8a 

III-  Curve  of  the  mechanism  of  the  action  of  potassium 
hypobromite  on  campho roxime . Grams  of  bromine  used 

up  per  unit  time.  11a 

IV-  Chart  of  the  structural  relationships  of  bromonitro- 
camphane anhydride.  I6a 

V-  Chart  of  the  structural  relationships  of  the  two  iso- 
meric bromonitrocamphane  anhydrides.  ^9®- 


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1 


I-  INTRODUCTION. 

Caraphor  and  its  many  co-related  compounds  undergo  numer- 
ous interesting  reactions.  Although  most  of  the  reactions 
have  been  explained  satisfactorily,  there  still  remain  a few 
which  are  somewhat  doubtful.  Among  these  is  a reaction  in- 
volving the  conversion  of  camphoroxime  into  bromonitrocamphane 
by  the  action  of  potassium  hypobromite,  which  was  discovered 
by  Forster  (2)  about  twenty  years  ago.  In  view  of  the  fact 
that  bromoni tro camphane  undergoes  so  many  interesting  and  un- 
usual reactions,  and  that  its  method  of  synthe  sis  is  so  unique, 
it  seemed  advisable  to  investigate  further  the  formation  of 
this  compound  and  of  others  closely  related. 

II-  'HISTORICAL. 

Forster,  after  an  unsuccessful  attempt  (1)  to  prepare 
alpha-bromo  camphoroxime  by  the  direct  action  of  bromine  on 
camphoroxime,  tried  the  behavior  of  potassium  hypobromite  on 
the  oxime.  He  found  camphoroxime  with  this  reagent  undergoe 
simultaneous  biomination  and  oxidation  to  give  a compound 
which  he  thought  at  first  was  a nitroso  compound,  mainly  be- 
cause of  the  fact  that  it  gave  Liebermann's  reaction  for  nit 
compounds.  (2) 

In  a later  paper  (5)>  however,  he  demonstrated  that  the 
compound  formed  was  not  a nitroso  derivative  but  a nitro  com 
pound,  in  spite  of  the  fact  that  it  gave  Liebermann's  reacti 
for  nitroso  compounds.  The  most  reasonable  structure  for 

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which  was  the  structure  assigned  to  it,  and  it  was  named  1:1- 
bromoni trocamphane  by  Forster. 

This  compound  then  became  the  nucleus  of  many  interesting 
and  unusual  reactions.  (See  chart)  On  one  hand,  if  it  is 
treated  with  concentrated  sulphuric  acid,  it  loses  the  elements 
of  water  to  form  a compound  which  appears  to  be  the  anhydride 
but  whose  structure  has  never  been  satisfactorily  solved  up 
to  the  present  time.  (4)  Under  the  influence  of  many  mild 
reagents  this  anhydride  changes  readily  into  an  isomer  which 
yields  a derivative  with  benzoyl  chloride.  Forster  proposed 
several  structural  formulas  for  these  two  isomers  but  the  data 
he  obtained  were  so  conflicting  that  the  question  remained 
open  and  the  structures  uncertain.  In  his  latest  paper  on 
the  structure  of  these  two  isomeric  anhydrides  (4),  the  struc- 
ture in  greatest  favor  for  the  first  isomer  was  that  contain- 
ing a ketone  group  but  all  the  conventional  ketone  reagents 
failed  to  indicate  the  presence  of  a ketone  group.  Conse- 
quently, the  question  remained  unsettled  at  this  point. 

A very  surprising  change  takes  place  when  either  of  the 
isomeric  anhydrides  is  heated  with  alkali. (5^  The  exact  mech- 
anism is  not  known,  but  eventually  an  unsaturated  nitrile  is 
produced.  The  structure  of  this  unsaturated  nitrile  is  fairly 
well  established  by  several  facts.  On  reduction  with  sodium 
and  ethyl  alcohol,  al pha- campholeneamine  is  obtained,  the 
same  compound  that  is  produced  by  treating  alpha- campholeni c 
acid  amide  with  sodium  hypobromite.  This  would  lead  one  to 
suppose  that  the  double  bond  would  be  in  the  ring  next  to  the 
methyl  group  but  if  this  is  true,  it  would  have  the  same 


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etructure  as  alpha- campholy tic  acid,  which  compound  is  al- 
ready definitely  known.  Further  facts  solve  the  enigma.  The 
unsaturated  nitrile,  called  inf ra- camphol enenit ri le  by  Forster, 
on  alcoholic  potassium  hydroxide  hydrolysis  gives  an  amide 
entirely  different  from  alpha- campho lyti c acid  amide  or  beta- 
campholytic  acid  amide  ( i so- lauronolic  ) but  is  readily  con- 
verted into  the  latter  by  means  of  dilute  hydrochloric  acid, 
showing  that  it  must  be  closely  realated  to  both,  all  t^ree 
being  isomers.  The  unsaturated  acid  obtained  by  careful 
hydrolysis  of  the  unsaturated  nitrile  also  changes  over  read- 
ily under  the  influence  of  acids  into  beta-campholytic  acid. 
This  unaaturated  acid,  called,  "inf ra-campholenic  acid"  by 
Forster,  has  a free  hydrogen  alpha  to  the  carboxyl  group, 
indicated  by  the  formation  of  a tri-bromo  acid  derivative. 

All  of  these  facts  combined,  point  to  one  formula  for  the 
unsaturated  nitrile,  'see  chart) 

Returning  to  our  nuclear  compound,  bromoni tro camphane , 
we  find  that  with  alcoholic  potassium  hydroxide  it  yields 
nitro  camphane  (5)  and  this  on  reduction  with  zinc  gives 
amino- camphane  and  also  beta- bornyl -hydroxylamine .•  Inci- 
dentally this  proves  the  position  of  the  nitrogen  atom  on 
the  ring.  The  pseudo  form  of  nitro- camphane  with  bromine 
or  the  normal  form  -with  potassium  hypobromite,  yields  the 
original  bromonitro camphane . 

One  of  the  most  interesting  and  unexpected  series  of 
reactions  takes  place  when  bromoni tro camphane  is  treated 
as  follows;-  If  it  is  allowed  to  react  with  alcoholic  silver 
nitrate,  it  is  converted  into  a compound  which  Forster  first 


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-4- 


thought  vraa  a camphene  derivative.  He  called  it  nitro-cam- 
phene,  (6)  althq^h  it  is  really  not  a camphene  derivative, 
according  to  the  real  structure  of  camphene.  The  main  in- 
terest at  the  time  the  nitro- camphene  was  prepared,  was  that 
it  seemed  to  open  up  the  road  to  the  preparation  of  the  enolic 
form  of  camphor.  V/hen  the  hydrobromic  acid  is  removed  from 
bromonitrocamphane , the  ordinary  type  of  unsaturated  compound 
is  not  produced  but  a trimethylene  ring  is  formed  and  this 
simulates  the  double  bond. (7)  The  so-called  ni tro-camphene 
has  many  characteristics  of  an  unsaturated  compound  forming 
addition  compounds  v^it  h halogens,  halogen  acids,  etc.  For 
instance,  addition  of  hydrobromic  acid  produces  the  other 
bromonitrocamphane  \vhich  is  very  similar  in  some  respects 
to  the  1 : 1 -bromoni tro camphane . The  nitro- camphene  can  be 
reduced  with  zinc  dust  and  acetic  acid  to  give  the  corre- 
sponding amino- camphene . This  with  nitrous  acid  will  give 
the  corre spending  hydroxy- camphene , and  in  the  first  paper 
of  Forster's  this  compound  was  thought  to  be  the  enolic  mod- 
ification of  camphor,  although  its  characteristics  were  very 
different  from  the  enolic  forms  of  various  di-ketones  and 
ketonic  esters.  The  hydroxy-camphene  with  (dilute  mineral 
acids  is  changed  readily  into  camphor,  but  displays  no  ten- 
dency to  do  so  under  ordinary  conditions,  which  is  rather 
peculiar.  The  presence  of  the  trimethylene  ring,  which  sim- 
ulates the  double  bond  was  finally  demonstrated  by  Forster  (7) 
by  causing  the  so-called  hydroxy- camphene  to  react  v7ith  bromine 
in  glacial  acetic  acid  and  sodium  acetate.  This  formed  the 


• \ V , 

^4  |i!V  J.i  ;>J5',  tj 

■>».:  s'  ■'  '•“> 


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(?'**•  ; n«v=  \t  ;jpt  ; 

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• 7/Pli.fi*;  •rf‘J  , i . . '4  VI.  ' ^ v< 

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4«‘‘  J * ou‘v*  ^ ^tnofxr;n«oI.v,'X?)iV3>^4  . 

, : . -.  • ,;  : 

-tv.-  I'V  w.t  J.rt;j,ji&tf4  #i*  ' ■•  * 5^  ^' ‘.^ ft.’J 'pc 

^ ^ A i*  .,  ■ ■ ' i‘  ■ ' fl  '«’’^  ’ ■ 

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,'  ‘ ■ > 


4,  I'.  "I ' . ' ' / A ‘ ■■'•  .--Bi 

V*  * 'i?  ’ i*  V ' ' ’ 

w 7 ■. • / xr . 5j«.  J . a ^ ^st t«'.  - \ ? fll'  - 1 »'^ » 'y  « 

' ' '»  ^ i’  ' : • '■ 


. * * 


-i  4.  g\/^  44?CT  0-PX  "tXi>Ao5 


:/:'  i.,  ' 4v.ia  # :V*  »: 


- I ^ .'iWtsiJ  ll/irVA;  .<?^'''5x  'CVlU>l? 


' /fjj, 


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•.«;h  (?iv;£j*‘  «rf'3  'i-c  tspxi<ic.fe'i^^M5^  .'4^i£v^Vq  _ 

■'  '''  . , ' ’■  '<  V ■>  •'•^l  'V, 


K? 


«/ii  ;:-,r  V«|’  nMv^^v\oAo*i  ©,*•  ^v’ 


i- 


- ..'  ■ ¥ , ft®*  . ^ 


I l|^...  AkftitW  t. 


i.vljt...  ... . 'h ."-•  .i-'o-:#! W 4.  ■j.Jii.-:-  r'.i 


-5- 

compound  beta-bromo  caraphor  and  shovired  vrithout  a doubt  a tri- 
methylene bridge  to  be  present  bet\Teen  the  two  carbon  atoms, 
which  ;/ould  really  not  be  expected  to  be  so  far  apart  accord- 
ing to  our  valency  conceptions  of  the  carbon  atom. 

The  position  of  the  bromine  atom  in  the  1 : 1 -bromonit ro- 
camphane  was  localized  to  one  of  the  two  top  carbon  atoms  by 
Forster  (8)  by  his  inve s tigation  of  the  decomposition  products 
from  the  action  of  concentrated  sulphuric  acid  on  bromonitro- 
camphane  to  form  the  anhydride.  This  was  performed  by  For- 
ster under  charring  conditions  and  he  isolated  as  a by-product 
from  this  reaction  a bromo- cymene , in  which  the  bromine  was 
in  the  position  ortho  to  the  methyl  group,  thus  proving  the 
bromine  in  bromonitrocamphane  to  be  on  one  of  the  two  top 
carbons.  The  tertiary  character  of  the  carbon  holding  the 
nitro  group  in  the  bromoni tro camphane  tended  to  place  the 
bromine  on  that  carbon  atom  although  the  proof  was  not  com- 
plete at  that  time.  The  formation  of  bromo-cymene  here  from 
bromoni trocamphane  is  very  similar  to  the  formation  of  or- 
dinary cymene  from  camphor  by  the  action  of  phosphj  rj^s  pent- 
oxide  . 

To  generalize  on  the  question  of  the  formation  of  the 
trimethylene  ring  among  this  type  of  compounds,  Forster  (9) 
tried  out  a similar  set  of  experiments  on  bromonitrocamohor. 

He  tried  to  get  the  trimethylene  ring  by  removal  of  hydro- 
bromic  acid  from  bromonitrocamphor , according  to  more  or  less 
of  the  following  order:  (on  next  page) 


.‘;<t‘-  ' .,'  . '..  j"'ii  '■'  " ' '^  '''  “ 

? •' 


. *.  r uK  |J^'4  Ji:4r  * ii  ..rnlSKiJ qs'  i' iiii.,<M^  IWo  J 


\ ,,  f-.',  •.  f»A  a - **  ■'K-’f^^'  , :?.f  ,^,lV5'  .f:i>Xflu,<  ' t''-)* 


V'-i 


'•iiy' 


• %d  BjrrJ.J  rcl^“-o  nv/  oVs^^i^  lo  y.,.-.^../  v..g^±T'^ 

^-■r  ^ 'v  ' “ , ^'  ^ 1 

■ nu|.r  ■»k4<|,  '**  4^ tr"  | V 

*-ra1  w .i.Dv;ao'u<w6i^^t  1^''^*"*’“' 

'-lifS  Ji  I**  I ♦/>  1»^jb  'dr^iw.;i  >U>4  4m'  i dfi^.o[ 

j,"  ^ ' f'' V ' ',  ' ','''<'^5^"  ''  '"3 

Oift  onc«o-i\/  kdJ  4‘-‘if*  ci  , ’;»•'- 1*'' o^'<? 

V.  . vv'’  "■  * 

r,'  f 'fc4iU?«c<  a/ 


v.'Oi  Cw't 

fc:  * ' . ■ , Tfh,  ' 


',AriK 


T-iilt'.^;  •i,^*  *0  t--  a«-svK^ 


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•■T'Y  /'  Tv^lriiA#^.  ■ , ...,  . 

V'  ’-'  ' 7 

r.^  •*  t » ; • ■’  ^ c'  '■'  1‘- 


. . ,,  tKtJ  aBv.I-q  <:>•  .vmJ  . 

**•«■'  ' • - t ' t.'  •'  VA  . rtf 


.'^i 


#ic»jr<  Ci,,  Ytt-  <\r  v«/l  jiltfr, ' ■'■  vot43^V'^iy-'5rt4  ,||jj 

-X6  'i'  Avij^-  -n.A%tv4f  |f'‘- 


I 


m:. 


■4.  'IX*. 


■ Th  ' ><;,' 

,,.j"'^,l'  ■ ■'f* 


* i^  i4  J.  fi -tv'f'* ;?! 'url  w/ 1 ' J'ft'  i!-..t  A.«  f<4 ' ■ A^' 

f "■•. ..  ‘ '-'» 


■ (.  •*■  t-aJlann^''  It wiiV-t'Vii?  " iSi't  f •'^ c 

' •*•  ' <■«’  ■•  ’■'  i'.''  ■'  ' ■ ■ ■ if >.■■•_•  ■;.“  > ■ ;■  !' 


IV 


‘ETjj: 


. 1'<1  /3  ■ ; - ' « • i'-' 'c.'t 'V , i'o  ' « i'?** *i’«  ♦ ■ ^ «?  4 yjp  t ■'i  f -i * ti^  » iSs 


I 


/ 

f •* 


O’*  V v4  '4^ 

: tti,  . ‘Jt t i Jt >•'«?■  y l;«iy ft 

jrifii'.  4 C >Ai, « % ,«?it;£'<i.  %i{, t':^4i ft ' 


(3 


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f«r, 


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,;f 


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C/t 


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c 

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c/f. 


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7y- 


This  would  have  given  theoretically  the  bromo-camphor- 
quinone  ultimately,  but  when  the  reaction  was  tried  out,  it 
v^as  found  that  the  bromine  and  nitro  group  were  broken  off 
to  give  the  unsubstituted  camphorquinone . In  other  words, 
there  was  no  evidence  of  the  formation  of  the  trimethylene 
ring  aa  was  the  case  by  the  removal  of  hydrobromic  acid  from 
the  1 ; 1-bromonitrocamphane . 

An  interesting  summary  is  given  by  Forster  (9)  comparing 
bromoni tro camphane  and  bromonitrocamphor  and  their  respective 


reactions . 


I 


f y *:  «■ 


- * • ■>  ...  . ' V ^ •«  ' ' f>‘ 

■*'->  "/  ' ^V''  ‘ y-'-'-^^'  '?V->^  '^'1 

Ji.  xiut  rol.n4  3*Ar  iL-*S.  l^■^l;<£^i}(j|^7^‘tt  ' 

r ' ' , .'■/'"n*.  -' . 

i *tf.  ,,^ Atr\4  i 1 «»  -t'ittn ct  1 i ti  b4i iij i^’Xii  ^ 0 e o^s 


'E, 

^ *riii>  "loWir  nl 


>"'■■!,  .;,  ■■■  , ';Vv>; 

• jtty  ,io  4%  ij.‘. ’tc'i  ^«*n.y  '>'• 


C*j 


\V  • 
^*1!  ' 5 »^  '**■;•' 

its  • i ■-  • 


its  ■*  ’I,  ■, 


''  'f  ''  , ' *’  .,  .’puj*  ' H 

^ \t  1/*  <j  > f ^ 

fV':  Tt«,r 't';  > ''^  Ji»Vtl  «/  ^ 


6 ' 


» - I.T  l!l 

, t;j»'.-i  «»^-i 

j *.  -m  \...  w 

• '..-  > "Hf'V 

4'r  .■■.Ji'^jfer  .,  'vi!; 

<•  - . '•‘If I i^• 


:t ~ -jsytjiiif:  I'""  Bi.'.n Jiim;'’iiuii.i 


-7- 


III-  THEORETICAL. 

Taking  the  mass  of  evidence  as  a whole,  that  is,  the 
compounds  derived  from  bromoni trocamphane  and  the  reactions 
involved  to  produce  them  , there  seems  to  be  some  doubt  as 
to  the  exact  position  of  the  bromine  atom  in  the  molecule. 
The  main  evidence  in  support  of  the  fact  that  the  bromine 
atom  is  on  the  same  carbon  atom  as  the  nitrogen  atom,  is 
the  fact  that  bromoni tro camphane  behaves  like  a tertiary 
nitro  compound.  Forster  in  one  of  his  papers  on  these  de- 
rivatives (8)  isolated  a bromine  derivative  of  para-cymene 
with  the  bromine  atom  in  the  ortho  position  to  the  methyl 
group,  thus  showing  that  the  bromine  atom  was  on  one  of  the 
two  upper  carbons  (if  bromoni tro camphane  is  written  with 
the  methyl  group  on  top).  This  bromo-cymene  derivative 
was  produced  as  a decomposition  product  from  the  action  of 
concentrated  sulphuric  acid  on  bromonitrocamiahane . Oxida- 
tion of  the  compound  bromonitrocamphane  should  indicate 
definitely  the  exact  choice  of  the  above  tvro  possibilities. 
This  was  tried  some  time  ago  (10).  Although  oxidation  under 
many  different  conditions,  with  nitric  acid  and  also  v/ith  a 
mixture  of  nitric  acid  and  silver  nitrate,  was  tried,  there 
seemed  to  be  no  definite  evidence  as  to  the  production  of 
either  camphoric  acid  or  camphoronic  acid.  These  oxidation 
experiments  have  been  repeated  under  still  more  widely  dif- 
ferent conditions  and  more  positive  results  obtained.  The 
main  trouble  seems  to  have  been  that  the  oxidation  was  not 
strenuous  enough.  Gwinn  heated  over  the  steam  bath  with  the 


-in 


"caV  ^riJivii'.  K ttJf  r»N3/tW»i'Vw..  ♦*', 

: ^ jJP  <■! 


f ! .-  M if 4.1  V Ci  l^i  i . <<  <\  ♦ V *»  « 

'V 


1/>L^  , 


if 


>l;r  *iK^T[Cf  Pw<  iUcl  #.i-  lO.f.  « tl '.  ",  «i/®-  .■!»  i v » <V 


’ • , - ’■  "7"  ■•‘■.V’? 


«i  «jec^tf  4^  c-'-c.n  ••>  ii«^A  citkiS%^p  «jsiri^«  &il^  xic  irJ^ 

^ ' ■■  J''  ' w 


.1  #iii£  «?Ai*Aw«[»0<>*t4‘«i;^oxjii>’Xcr 

i'-  ■’  *•■  .*♦  ••■  •,«•  ■ • •>  ■ ‘ '''J’';Vr  1^',‘Y,  > 

-i  ■ ‘.  . . , j . ■.->  V>  "w5^”  ' , 


IS 


■'ii'  Httv^  nc  r: 

'•V  ■ ‘ 


j,ap»  ^^“SJ  jfn 


‘.I" 


*<(  ■j*^8»4  lo  ir^'. V o (-S } 4»Vi^jt»vit 

" • ' '■?!  iv-  ■ 'i. 

IvdiirCir;  vaJ"  cJ  iTa>.f'’ir’o«  -*»>},-  ^ 

■‘  '.i  . V'  >'T^v.  - .. 


t*ajj  '»* 

BiU  •.^I'a  Av  L f ; rf. • u,- iv* . T-'  ■’'* 


d;i. 


rx**xJ*tv^  -i  tJ ixvoflioid  tiv 

' ^ ' 1;^::  '■  ->#■■-■/. 


ov  i-'Ay!!-?  4»t"' oi;>,  , •.<;,oJ  fio,-  , 

'*.‘r  • i»  • * V^ ' 


' *1  ' ^ '''.?'^i4  ',  <f'j’  -'  . 

to,  rte>*J4f4  >iU  >tgi,^  ,itfti-^jt‘i*i  xioX4  iflOs.T ‘ O*  f>*ox*ib>C«|r^.<^ 

» i _ I ’ ^ 


-f>bl^i}  .mA  xto  blow  J^obaco 

' '■  ■ ' <S?'  ' >'  ' ■' 


' ’■  " ■ ’ .'■  .•  4-' 

, ; N£  ..*  /,  -.  i y . t 

O'*,!  I9VOOV  ftA-  t®  Bt>  Lc  Ao'  itjfixn  ^xi4" 


^ ^JCC  uaucff^/w.  4 ■ ■»  I ©Jlitf*  ;■ 

■ ' ' ■ ' ' .•  ':l'  ' J*  ,-  , . *'■  *.'. 


■r  ■ ; r ' ■ ^ * 

■(  ?'Jt-T.  unl-^  bif*>  i>Xiir>  ilJfytK  ^arr 

^ ‘ '.f/'i  ^ ' 4 ' 

o-.&xfj  ' -4i>li  'iWi'i  - ' *v  tt. 

; , .,  I.'"  ” .\'i 

Ujii*-'  ( ♦Jlaitol.  OA  'J<d 


► Tif~ 

ir  . i-  -y'  ' . , . ,TrA<*l  '’■''  ■ • ■ f? 


r fi  T7 


ri<5«  rnj*  Va'i  n*i^Sv.ti  <»oo^  £!<»<»d-  Av/aii  ? 

■ .',  ■ ■ 7.  r 

• j-ci(  /J Xiti'k  bf.4  «booo  J-flvaOl^ 

" ■-'‘'"•'  , *C  ,^'  ^ 

^04  ao  iTktt  ' V^ixJ  hV.'Ui  iJ  »jSO®l*  .1  >,  '.'. 

f.  ' .,  ' ■ ■■  ■ J 

V c ■ • ' • 

■ ';  ■;  ' ‘ ^ ' r ^ ■ ;v  ^ ~ 

'4 


ai«5:*s*w5a;fc- 


: 4>  i-*fV 


-6- 

oxidizing  agents  for  varying  lengths  of  time  with  the  result 
that  there  was  almost  alvrays  some  unchanged  bromoni tro camphane 
remaining  in  the  condenser.  This  probably  contaminated  the 
oxidation  products  which  indicated  falsely  that  a bromo  acid 
was  obtained  by  the  oxidation  and  further  indicated  that  the 
bromine  was  in  the  opposite  position  in  the  molecule  of  bromo- 
ni trocamphane  . Accordingly,  the  oxidation  has  been  carried 
out  by  the  use  of  dilute  nitric  acid  and  constant  refluxing 
for  approximately  a week  or  more  in  time.  From  the  long  time 
oxidation,  camphoric  acid  has  been  definitely  identified  and 
also  the  barium  salt  of  camphoronic  acid  separated  from  the 
mixture  at  the  end  of  the  oxidation.  If  the  oxidation  is 
carefully  controlled  under  certain  conditions,  it  is  possible 
to  isolate  considerable  quantities  of  pure  camphor  as  the 
intermediate  stage  in  the  oxidation.  All  these  oxidation 
products  go  to  substantiate  the  formula  for  bromonit rocamphane 
which  has  the  bromine  and  nitro  groups  attached  to  the  same 
carbon  atom.  This  is  to  be  expected  from  the  synthesis  of 
bromoni tro camphane  from  camphoroxime  by  the  action  of  potass- 
ium hypobromite. 

In  ^he  last  analysis,  the  formation  of  bromonitrocamphane 
by  the  action  of  potassium  hypobromite  on  the  cor re  spending 
oxime  is  rather  unique.  Bromonitro  compounds  have  been  made 
by  the  action  of  potassium  hypobromite  on  nitro  compounds  and 
bromoni troso • compounds  by  the  action  of  bromine  and  sodium 
acetate  or  pyridine-on  oiimes,  but  as  can  be  seen,  the  syn- 
thesis involves  both  bromination  and  oxidation  in  order  to 


I 


1 


, V-  -■  •(;  . -.i.  •%  / , ,■ 

"-i-at,  . ' >■ 


I 


S'^'^  > i V V»%  ■\UiiCrl4&dt  .' 

PT'-  -/  ■ ^ 

?LA’  ,^t»i/7  M/U/  it' 4S»?  tit;  X 9'Jt^  . 1 t tr  (jhskOi  01>M  % ityr 


Wi 

I ■..s.-iu*  3^fj  ^ ^ r . i.  t<' M>*' 

‘>1^^  *;■.  ‘ ;^--.3iV.,,'  ^ ; ,, 

r«i‘.-li  v*A».'C  I ~ 1 'tf 

'j-  4 1 ^ » ! ;gj  - .,,  ' ' i . -f  = 

*'  . ' ^ ‘ "’i  '’t'  i 

>, ',  J ' «r».  cn.t._  . , v*>.'  I9..  ^ 


/ 't 


Jg-:  - ; . • ^ (-  t,  'Td  ■ ' 

^:slt  '\»oi  •s^T**'  is  call  “ , '4V  ’'^’»V'^  ^ \ <fcj»;,TlO‘‘l 

, - ■■■%.»■.■.  . 


, pt^4  hrhin\:c;»^  ^fitivs-:  K^f\>-i'Jii,  1.  \-c 

i 


ol  'VI 

•liArj.ii:  f’44.  ' 

6fi‘  .‘*  t'oJr  ^ '1?  rj 


\ I ', 


:<?  'VI  •./•riia;Ai.*o  •'ic 

-^  ’ ■ ’ • ' ' , ■"#  'cJcVjHv 


. - . ■ , •.  ,,  ’ vVT<  ; -:  ' i 

J.,  J»0l'.’ifcJU/:^O  -C  V^.J'  -CTrt  . n:i'  ttgaia'^' - 

•'  *■  . • r ''*,  /,  ' •■  ' ' , . '^.,  . if^  , -,‘.ilil  -r^v  ‘ ■ *4 


v*:-.-?ii  ;'i4.A<f  5viiU  . vliv  ■;,[* 


tf'.^  viiu*tic?44;d3  f»t#'J|..  MT  <^''- 

--  '■  ■ ■ , '^'  ..  ■ . > ' ■'  ‘ *"  • ■‘'■3  y . & ■ . V"  ' ' » Vv‘^ 

•oi  xVf /»' /.fi.'i,  ^nTiAa^'^<^  - vcj  t>i./.4j%,:*oi»' 

-»ii'J*  ' ■ ■*.■>*»  (iWai  '“  ^ * V 


^ , 

« ,-.  i-v: : , ' ■ ■ ■ ,, , jm ;,  m 

’^ ''  vW«yw  V\ 


Lh^j 

/ V 

A.  •*,■;.•.  • . - 


ijb  1 d 


:.Va 

») 


(ail.  X ■'■/•  ■>>/:-.ii.,.  ■ 


-9- 

produce  both  the  bromine  and  nitro  groups  on  the  same  carbon 
from  the  oxime  group. 

Forster, (')  who  first  synthesized  bromonitrocamphane , 
suggested  that  the  oxime  is  changed  first  to  the  bromoni t roeo- 
camphane  and  then  is  oxidized  to  the  bromonitrocamphane . Since 
a green  colored  compound  is  invariably  produced  on  addition 
of  the  potassium  hypobromite,  he  suggests  this  green  compound 
is  bromonitrocamphane  hydrate  which  on  exposure  to  air  loses 
water  giving  the  final  product,  bromoni tro camphane . In  view 
of  the  fact  that  this  reaction  is  so  unique  and  it  produces 
a compound  which  is  the  nucleus  of  many  other  reactions,  it 
seemed  desirable  to  investigate  in  detail  exactly  as  to  the 
mechanism  of  its  formation. 

The  first  thing  obserived  was  that  the  supposed  green 
bromoni tro camphane  hydrate  was  unaffected  by  the  most  vig- 
orous dehydrating  reagents.  If  the  impure  green  mixture 
produced  by  the  action  of  potassium  hypobromite  is  taken 
and  treated  vvith  concentrated  sulphuric  acid  in  the  cold  and 
then  finally  steam  distilled,  a mixture  of  camphor  and  bromo- 
ni tro  camphane  is  produced.  Simple  warming  and  steam  dis- 
tillation always  yield  some  camphor  along  with  the  brononitro- 
camphane.  Phosphorus  pentoxide  and  phosphorus  pentachlo ride 
in  a boiling  solution  of  the  green  compound  in  toluene,  ben- 
zene, petroleum  ether  exerted  no  particular  action.  All  of 
these  facts  united  probably  shov/-  no  hydrate  to  be  present. 

It  was  next  conceived  that  the  green  color  produced  might 
be  due  to  an  intermediate  bromonitro socamphane , as  the  green 


^ r;^ataa^■^w^a;^-  ,>a»ars 

‘ 4i/7>  >:mm 


JRC<^  t ' 


‘Mft  j 


" <• 


' ^Vl  ’ 


'f;  j!» .'  <jt^  ', 


, . it  If-  * -s' . 'X':  .‘  M. ' 2.W  tl 

. <.  /:ikm  ■•! 


1?  L t 

^ I 

■■WAv 


r .?  t%  i n t 4r.lHu 


■^s, 


• ct  V sw /lui^  vi^  i'«i4i^  ‘ --  Vi’^  t »n4l?l|»o 


^ - '■>  ■ ' .:iA^ 

« >ii's  <-.  i^vA'i  f i JC)« '<■•'  J "V 


tf 


Iau*.' 


K Sir  t v'o-#!-,  QirtJ  nii  i'i»J6Jo<l  -*jCI'^!-5.)C) 

-*'■  i;  ’’■■  - * -■'  '.  n M-'' 


t'mtoj  tit  i*  :.iJ‘>  • a /ii  eci^ji(^ib4'';Ot^T54'^ii'vfcoid’ 

.fkit^.sri  . ■^  ,■ » ,» Bju;  dis4'  Xaniji  tv#A<<f 

• .'  ■',  ■ V,  V ' ■ n . ■■  ■;  tr ’-Ti  ’■  • 


9Jii  hua  u0  n-Jt' r e|w.*,  a'o*v  i»ffj  /r>  1 od^*  *'?f 

■'  >-  ' -.'  - . ■ 
i ; ' 'I ' '■?•'« 

J-i'  ^ f uoif'0^4*-.  ^-iwcav  '4$  <-  *4' '- ).  »I ->  odx  »'l  ,riwtZ^*f' 

.».._  k ".Jl  ■ --  • ft  I JP  >■  '"  aih 


_ .JWl- 

V « 


: ; fliO  xij;  r»»* 

f%'*  ■'  ' 'ji '*■•  1 i'''''is-  ■'riP'R''?  X 

■■".';  ■ '!>  . ''  . \.-v  .■:V-'i  ...  ;^‘\iki«,-. 


J 


iHtio'X,,  /.>#«<(. f;fti?e.  a/A'  : 9 0 (t^  'J--T:7r^^ 

2i±'*  yi»  ni'.'  Jj«2  t'  '4*  «/  i4fcs;i!w4rCr -.'i 

AVI  ' ‘ / 


I?- 


t 'i» 


t»i  i/  J^  ^ z j 4>  irl'a,  L 


f«  1^ 


•;  OJ 


If  , (.,  ..  itf  '.. ■ ^^«  .■’ ■■ '*fl!-  ‘ 

rt-CUA  lJc/’  ♦Vij'  *0*  a ^*lX  «t^*uo0i‘q 

* / ^ * < A * 'll*  ‘ 


-f?!;,ctid  luj  If*. 


-.J-'t  r-r  '#S^.  11 

If*..  ‘in  iHu>'KJU-  i»  , 7dSl  = 4'i^4 Xb,  „nl 


V -tJXJ-  ;'■  itAlo  '-:r.'  . .i/.  ; uW  ‘<rorta  . :»t»J5bjbo:t<^8 jfeU 


'■  J-  •■* 

I* 


■ - -"■'  ■'li"'  ' t'i 

-f  t*,;utuf  ■!■?' »|iJ  li.f'jv  ;;il0ll)  •^oH•;/  .*^  l/cv»  IvXoi  v » tjtj!,  "T 

> ^ ■■  . ...  V';'"  '.,.''3  ■'  ^ • '■'  -L-'v 

-ftlAiTcixi v'Moif*  ofJ»rf^ 

. V»  - 'Skfl.'*^  ' 

V/'-  '■'.••V  .''  ' 

X/ xU  ^ 0 'tij  >>nvo/->»<.o  aci-9«t.j^;  t?^4  ^*t;c  <»*:■ 


* • I*  6 •/ cf  . 8 ^ fc4'4  itfta 

"V  '■ . ‘ \ 


•’  - -V  ■'■  ‘ ’ \ ' • I 

.'-ft  J'V ttiXci  <*  '■  >»  J 

- i ifiX  . r 9 


*i^  . '{%  gi'.J  r a'  ^ >***^..  iLii fida ce 


V ■;  '/^v  . ■'.  ^ r 'ki  lNw 


■ >’y. ' -’  — 


- 10- 

color  is  characteristic  of  these  nitroso  compounds  in  this 
series.  Accordingly,  attempts  were  made  to  isolate  or  prepare 
by  some  manner  or  method  the  intermediate. 

Piloty  ^11)  prepared  bromonitrosopropane  by  the  action 
of  bromine  on  acetoxime  in  both  sodium  acetate  and  also  pyri- 
dine, So  similar  experiments  were  run  to  prepare  the  bromo- 
nitro so camphane  but  there  was  no  action  observed. 

The  next  attempt  to  prepare  the  hypothetical  bromoni tro so- 
compound  v/as  by  the  use  of  the  theoretical  amount  of  potassium 
hypobromite  necessary  to  brominate  but  not  to  oxidize.  Al- 
though the  reaction  was  carefully  controlled,  >.he  final  result 
was  that  approximately  one-half  of  the  camphoroxime  was  changed 
completely  to  bromoni tro camphane  and  the  other  half  remained 
and  was  recovered  unchanged.  This  would  indicate  that  the 
oxidation  potential  necessary  to  take  the  bromonitroso  compound 
to  the  bromonitro  coigpound  was  less  than  that  necessary  to 
take  the  oxime  to  the  bromoni tro so ' compound . 

The  final  evidence  which  led  to  the  abandonment  of  this 
line  of  endeavor , i . e . , the  isolation  of  the  intermediate  bromo- 
nitroso camphane, was  that  obtained  by  the  quantitative  obser- 
vations on  the  course  of  the  reaction  between  potassium  hypo- 
bromite and  camphoroxime.  It  was  hoped  that  the  course  of  the 
reaction  might  be  the  immediate  formation  of  the  bromonitro so- 
camphane  and  then  the  slow  oxidation  by  the  remaining  potassium 
hypobromite.  Quantitative  amounts  of  the  reacting  substances 
were  taken  and  the  course  of  the  reaction  followed  by  the  re- 
moval of  aliquot  parts  of  the  potassium  hypobromite  solution, 
addition  to  potassium  iodide  solution,  and  titration  of  the 


V.  T/ATV  -I-  ' ■ ' ■ .•.  ‘»T- JWW 


*,  ■'  .*;  » i5»  *1-  I ■ - 

’ M hf.J  si.!:'  e-.  0^  o¥o'f  w o<»  ■'*1^4  / 


<■  t 


0*4  ■ ■'— : tj,  ■‘t  K '■  ;>  • *4*)  t'i oi^: 

■ ,1  *■  ‘V 

■ I •-  m'  . . , ‘ " ' k M * i 

■T'.,  , an'i*  . vUi.4j.OA Xo  (#4l0e  , 1CP 

■ ,’:■  *;*  '1  ■ ® ■ ..■  „ •-■.  „ /., 

V ' vl •■»<?. 431' *><W  X- 

n '-■'  '■'  ’'.  ■ ,-  . . ;'j  ^ 

tpp.'u'  J «i  »'*.'i-.i4..,04«Ht».-*  *<v„  «o4ir  of^J:  ,*t6 

' ;.  ;■■  rr  ;■' 

- ,>'<  "-■  >-  « “it  <s  ''■'cT^* .<«>'  . a'»f  ■ -*  J-,j  4(1; ; i « t, i^'i/ii 


ji  xofoaf.  ' i 


I 

II 


. ij-ovi  M»c1 


;,  ’ . ' . ' 1..i  Vv-? 


i 


r 


'JMl!. 


Ito  uii/ro#J^  i’ * - ^<v  tt*»j.  btwc.^(jia 

' ' ' r ■ ’ ' L J -Rl’<^*‘  - ' * 

.a-ai-lJCf-  iiJ  S(i.-.  } 4t4  w4  %‘'is^Xif.U'J9h 

* • ■■''  "■  ' ' «••  ■•■.!».  '■  ■,'>■:'•'■  I, i 


'^.''  ''ivi 


itf-  '.  vXJ  t)  .rn/k  i»  ■6m-h  aul^i>4»01^v«cl4 


'4-v,  Vf%  f^■^-  ?'•  t'-ic.'  l»tf  IH^  *c  *4.^  » 


'UlU  t^^iU  V .«4.>  ■ t.  r wa*''4r,s./.t'.CT^JiitV'VOX'l->oS 

•#^  ••'  'v  ' ■.  '**■■  ' •%.  , ' ■ • ' '■  , V 


A.  » 

T[  ■ 


* ' - 4;,  ’■•  ‘ ■ ■ T>'’  ‘ ' ^ '*^ 

tr'.  ■ 'a 

li  ' * -■  ' -ii  . .- 

P*  =H,.f«f4V4  ^c.  J^Tv'Crx  vi(»<fj>  \borf  CJ  t- y*  uuiiAiic.’ '9«froja 4-sir 

'i'  V ' ' ’ ' ■ ’ ■ r M 

* ■■  < • '• ' - I • 

B -otK  tcj'  ■ .'c>3^i  1 0^.  iHJirl  iV  ^(.  - . of  4-  oi-:;^  , . a,  i \ x 

■'"4 -'3!^  .'•  ' ® 


ff“w  " ''"  ‘ \J  , ‘ '>^  ■' 

II  K.  - c-fi’\f!.  tr^4oij ^4;<«  o'oi^k  I'di  lr<i 

I i»Ha  I"  *.*.■' *: J O. c-  *>*4  ■j.-adA  .^»jaiTj>CXon^i^-^ 

•V  . ' ' t ^ ' ^ ' . /«' ;v ' ;*1  ' 

•i^fel-' 2^;.  J.c-'Mf  ic-. 

'i  ‘ . -.t.t  ' " ' ' '1*5^*  ' 'y;^  ‘ 


,f 


1 


i^c  44.51:  i>o 

Ti' , ~ ■ . .1  1 ■'■  i'.'  ' ’-,*'>*■'  » 

fjt  b 'i  a ii>4  e cf  t»  . «» ft*  'T“  1..  C ^ M ii , ,<ikY  I P ^ .'  • 

I . ' . ■ r:„a  ‘>vf‘4fc,'-.,  'N-v 

II  •Miy'i  *rl\i,  '•i.f  .K^Vn' C J 4^'l  $ i ^ m<A 'o  '><111  >V.  - 4c.  v.j.'j,  « ..4  rl’'«  tw<fa.  . i 


■«f£^  ItfjoJfiijl 


Y4 \ ;#lf  "jy' " , 

^ Xjiitc^rV-Y 

I’Jf  noiv)i^‘i4  4,4  • t'XJ4'  xp\.U^-lViJ 

I uA-^y  ' ' ' "l.  ci4i 

M 


sisr  . y.-^.  .»-.{acatid»?3 


- 11- 

liberated  iodine  by  standard  sodiura  thiosulphate  solution  From 
the  data  obtained,  it  is  a simple  matter  to  calculate  the  grams 
of  bromine  used  up  per  unit  time.  In  the  chart,  grams  of  bromine 
are  plotted  against  time.  The  actual  curve  obtained  does  not 
show  any  break  whatsoever  at  the  midway  line,  thus  discouraging 
any  further  attempt  to  isolate  directly  the  intermediate  com- 
pound in  the  reaction. 

Since  it  Viraa  impossible  to  prove  bromination  of  the  cam- 
phoroxime  took  place  first  and  then  oxidation  by  the  potassium- 
hypobromi te , it  was  deemed  advisable  to  eliminate  all  of  the 
possibilities  except  this  one.  Theoretically,  the  bromonitro- 
camphane  cs.n  be  produced  by  the  two  main  routes  from  camphor- 
oxime  by  the  action  of  potassium  hypobromite.  One  is  the  route 
just  described  aba ve , by  the  first  stage  of  bromination  and 
subsequent  oxidation  of  the  nitroso  compound  to  the  nitro  com- 
pound, and  the  other  is  the  reversal  of  the  above,  wnich  is, 
oxidation  taking  place  first  and  bromination  last. 

Accordingly,  various  experiments  were  run  to  attempt  the 
synthesis  of  nitro- camphane  from  camphoroxime  by  oxidizing 
agents.  If  the  nitro- camphane  could  be  produced  from  camphor- 
oxime, then  it  would  be  a simple  matter  to  obtain  the  bromo- 
nitrocamphane  by  bromination.  Theoretically,  it  is  simply  a 
question  of  which  way  the  intermediate  molecule  will  lose 
water  or  potassium  hydroxide,  to  give  on  the  one  hand,  the 
hydroxy-nitroso  compound  and  on  the  other  hand  the  nitro-cam- 
phane  or  its  pseudo-nitro  form.  Examining  the  situation  still 
further,  it  is  evident  that  the  synthesis  by  this  method  would 
involve  the  transition  from  a negative  nitrogen  atom  to  a 


W: 


' f 


tt'  -■^’i  r.-^  ~ia^  \ U ‘it 

. ■ . ,,  ^ . , ■»,  ’ Alt,  - 

fiJ  ’ iT  c-'Vk  Xni.  ;>>'<•  ♦'i-  . 


r ^ 


% 


r 


'4' 


•]Hx  frv. 


■Xj 


^>iii  JUit 


I * 


,<:ii.  2.- i.  f «*:  <f!TC ‘^f?  (i‘ 


it 


,.  ■'  i j •*  ' 1 ^ ‘ ^ ^ ^ 


I' '\i 

. '^"  ■■'■'^  ,ita^.i-t^ai^  d\ 

■-A*  '■; -- '■' 

^ “iNf  c » f*{j:  ■"!  <i  oi^tJ  i : 


4.. 

I 


K 

■■>  t 4 'J  -'  > 


C T*  UVi)Tt<l 


e W 


'»'. . .. ). 


v'-.i.  ..MOZ.,  A.i^  ,/J  <l 

z: 


-I'V  j/**!'}  i -:m  ?£^^isi3tc^ 

. J-.  *j  ■ ' ?'  •* Mc  ^ JH!'»‘  •*■  ^ 1 ' 'idts^K ti 

V*’  '^'  '.'■"J^'V' 


I if^'f  *x  S-TiT  1#*?v 

n 


'('H'  ■ /'ji*“"- 

:«j»a 


0’ 


* A 


'S'fi 


c-a  -_o  /f/. . U (r  i , V^ 

■ ' ■*  ’ . . /I?;.  • 


V r 


>( 

[(•; 


,#z  Ho’i  >,  . /avftrfr.  •■.i«>  l6  i' Wt:  >-V-^\  r aV^  VX  ' fc«-«i!r*‘|i.„ .' 

P.  Bib  — ’ ••  '-F' /.  . 

;»  - .i-5 pi*  rt-  fiaV  ♦ ;t,cx4J  -n  «^«li|'^'’' 

P-.^  ' ' * ’ ' ■ T ' ' ■ Wj^3  » ■'  i * •■  ■'  n ■ 

-j-i-i  \'j^S ‘<, ■■$'.*  tiin  nJ/i&ri-f«v,  n ^’€»5■f>*  ' ' S 

[A>  ,••■"  >*  J/.' 

S''  - ‘bl-C'' Yi  axi.  t^-%v  I.  ..'i^x*,  Vil'i-^  '*0  ♦^^;|(»M^''Orl^;,V''  'i4 

^ .,f'.  ;■•  ^ : S'  ■ •..'»d'  ' ■ ‘-'^al 

"?,  V-.  .V  «.  . # 


- i<..^.-»i*  ^ ■ ...;A  t..5Qii(c,  .fv,  :>  f i o ' iit^,  ,.,.  1^'  tu'. 

fe>  n.f fU.»JxS.  »*  * ,.o4' 

■ ■' .%  • :;'3feyl 

-Mi  J-i  »•.,  • wi ' iw -to »47-. ■■  J 

*■'*'  '"  • -a';  V’X  < r • ■"’  ,<£■ 

^':  '.t  xr^,;  »tv  ".U'^ 

^ '-  S';'  .',  »'  .tt  ''Vl- 

.••:'♦  , 'M..#:  ...;:4  •4j4^  hc‘.- 

. ,,\*  , - ; ,/  If-.  V ' ,’',*A;vA 

,,  :«';h/*u-^»uxn  ijj3.  .'.inazf 


' .,; 
'i 


X)'.)’- 


Wi  ' ■ • ■ ■■ - ' ' vitSr-rm 

i.wV.' J,i  ^W'ila  r»'Aj<!.'JC^  ■ >-«iiri& 

i"  *:■ " J"  .'.  K '±<A..  ••■•-  .a' '.'  j ■ '>tK.  . '■ 

liUoH  f ukiQ^ti  nJiuvj^  Y,<.'  >il-  i>#4i  ijr>i'«iV'>  «:  #i  ; 

" ' -•  -y>  ■ T. J ' , ./  ..  ^ ■’■iui“^.  ,r 


„j|'  «. 


-12- 


positive  nitrogen  atom  in  the  nitro- camphane  and  this  would 
hardly  be  expected.  The  actual  facts  from  the  experiments 
bear  out  this  expectation  that  the  change  would  not  take  place. 
Oxidation  by  dilute  acidic  potassium  permanganate  and  in  another 
instance  by  alkaline  potassium  ferricyanide  produced  in  both 
cases  an  hydroxy-nitroso  camphane  which  was  first  prepared  by 
Forster  (12)  Furthermore,  neither  bromine  nor  potassium  hypo- 
bromite  would  transform  the  hydroxy-nitroso  camphane  over  into 
the  bromonitro camphane , This  eliminates  all  paths  by  which 
the  camphoroxime  could  be  oxidized  and  then  brominated  to  give 
bromoni tro camphane  , leaving  the  route  whereby  bromination  takes 
place  first  and  oxidation  last.  Knowing  the  above  fact  , it 
was  possible  to  so  plan  the  reaction  conditions  so  that  the  en- 
vironment would  be  suitable  either  for  the  choice  of  one  route 
or  the  other.  In  no  case  has  it  been  possible  to  so  control 
the  environment  so  that  the  potassium  hypobromite  acted  solely 
to  brominate  or  to  oxidize,  but  it  has  been  possible  to  make 
either  one  predominate  according  to  one's  wishes.  By  suitable 
regulation,  it  has  been  possible  to  produce  an  almost  pure 
white  product  by  the  action  of  potassium  hypobromite,  with  only 
a slight  trace  of  the  blue  due  to  the  oxidizing  ©ffect.  Or,  on 
the  other  hand,  it  is  possible  to  make  the  oxidizing  effects 
predominate  and  the  greater  part  of  the  product  will  be  the 
hydroxy-nitroso  camphane.  It  is  evident  from  the  above  data, 
that  the  supposilion  of  Forster  that  a bromoni tro camphane  hydrate 
is  produced  is  incorrect  and  that  the  green  color  produced 
which  he  observed  was  not  due  to  the  hydrate  but  to  a side  re- 


'•ia-  ■ » < 


7' 


( ■ */* 


'ij.  :i^y  ■ ^ 

.■'.;sj'! 


'I* 


P ► 


i 


««  a r ^ * 1 ^ 


:S‘  t' 


j,-,t.*ff'*w>'5a>»ii(i ‘‘'S *-■-'  ‘7*r '*  X^Kv'‘4  •oCiT  i j*f  :*-«  1^4 

■ '^  ‘ '■*  " ,1  V . •■  r -fi-  i..,  ••  't  < ' 

yi>ir«  : J ;AnA^./' . i;'>ft.*I*v  *‘ 1 

* '■  *•  . ' " f,  . i <i<  2i  ' ' - J 


H!  ir  '"' 

^ fc49il.‘  .1C  0>ii»  ,:<u  iittf’X 1kJi.H3i'-^9i\4  ^ ' 

'j  -.  " ‘ ■'  TO  ' \ . T 

(s  .’i'^ 


. ■ ■-  >•  ■ ?•■  • , '.'%^<»  . iiWsv  •• 

'>••■....  v%ayigii4»j:0c  -},<^  I v;  4.' fit  fell  <ri  iff' 


«cn<  i^yp  c*«' -ntX  ’T*  tAx*' * t ftj4?  wlio ""Aik O'*'- 

♦ '*-’^1, .» ’J'X  ■'•  ■ ■ • wr^  / 

' tl,&*..v.  v<r  '^rtvi.atl  f I ii  r&»‘ «i 45- 

^ ■ '■ ' ' ' '^'  '.  - W'  "':'  ' '(7^  , 

. ov.?_.  ' .*  V.»w  <#£[ZtfC(i<r  .'.&u;  * .M  *'i..' .,%4«r 

iXMi' .' •*■/».' 

■ ' . . - V. 


'i%  2 ic  ^ its'**i  »Yc<j;^  f*’'?- '<M.  :-ji,s'fit’  .-,.;tt.l  (C/oZ'i  44*4X0  /4^it. 


^ 0fiJ  jitd-i  01  . - iil»v  f4**'40A.^*i  *>t{y  ,it,‘Tf  tii,- ec ’'^y  * ♦ Icfiaapq  ’.ioy' 

^ ‘ ..  ^'  ■ ' ''.‘'ivu  f " ' ' ■ ' tV^v 

I 1 < ■ jf’A'  * 

^■^-'  o.Af>  I4:  tptclifi  '♦rf^‘ rri  vy»t>’Zo  .Hf..(frr«of 

I ‘ , ■ %■  ;-.  ',  '.11  ‘ •..  I'  fi" 


1 >'•/  ui'i 


I i tJa  fi  cX,  - i Z a®'  ^'ii.  -. />u  ■ o«i)fr  ^htt  itJ  . •* * i#dF#- 1 

' • . • ' ■*  L'^"  • ' '*  ff  'x*  - ’ 

\lmtoA  bp  ^ \ Jl  W ’ y 


,’i.v.l^  ; 


«V-’<4  /i.  .1  l«O0<<  wSV.J  . ^'.i.4  ,w'i. 

‘ ■ k'.’^  ' ‘‘  ' 


\ pX^A.Ui,  a'"  V.3  te'.up^-  oJ'  i;a4ir..xciaiti 


onfV^y  JnpiaU  n-'  »t»i}*  o..  ,;..  ^idlaapt*!  utAtT  a A 2L^,  ^ 

' "-  ^ ’■  . i . . ‘ 


r' 


'1- 


XTr,t'  i^XIv  •:ij- •'.  j <^.^»v  tii/j:.ti  u<^'  io  ••44^’  C’l  X4’' 

'''  . - . -■■■•  ' '*>  ^ ' f!  * 

Jtrv  v*;C  laKi  • V , ’‘rt'J'  '“14 

^ ^ V „ - ~ ' ' ' '.''"lir  ■ VI 


o« o 1 Mtiibstd  >*  ! 


’.  rfi.  o-i  ,£Jfn 


■r4. 

^ t 


Af*.'X.5  i.ic.1.1.  X;Vi».^-£t.'»..8'i  , 4 r .f’lri'iw 

f;”  ‘ . '‘M-'T . ' '.->'  ,' 

,w-'  ..'.  ‘srt  *»  JjUW  1 


Cf«OX^'4b>SfApii>^4  --  f 

'^'■1  !i 

aoZj  , 

I *|/v*"  * ' ^r*J|  '"SC  ' " 

1. 1#  0 Ji  *'  ft  *1:  a 0 , ^ ^ ^ ^ 

‘■■'  '■  '■  9 . ' ■ ■ ‘ 'j-:.;"''  V. 

y?»clr.‘"«4’N'  * 


^ i>i  J'ijti  4 pa  itisn?. 


.9’ '*4 


-15- 


action,  the  simple  oxidation  of  camphoroxime  by  potassium 
hypobromite  and  no  bromination  of  this  side  product. 

In  the  original  work  on  bromonitrocamphane  and  its  many 
co-related  compounds,  Forster  prepared  a compound  which  he 
named  inf ra- campholeni c acid  and  this  was  made  in  turn  from 
inf ra- campholenenitri le . The  nitrile  can  be  prepared  by  the 
action  of  concentrated  sulphuric  atid  on  bromonitrocamphane 
to  produce  an  anhydride  of  unknown  structure  which  with  alkali 
breaks  down  into  the  inf ra- campholenenitri le . Although  the 
structure  of  this  unsaturated  nitrile  seems  certain  from  the 
facts  as  presented  by  Forster,  it  seemed  desirable  to  subject 
this  compound  to  oxidation  and  examine  the  products  so  as  to 
have  additional  evidence  as  to  its  structure.  If  the  structure 
is  correct  according  to  the  formula  proposed,  on  oxidation  and 
hydrolysis,  it  should  give: 


The  unsaturated  nitrile  has  been  subjected  to  oxidation  by 
potassium  permanganate  first  in  neutral  solution  to  make  the 
di-hydroxy  addition  product.  Acid  oxidation  can  not  be  used 
as  mineral  acids  cuase  the  double  bond  to  shift  down  into  trie 
ring.  Accordingly,  partial  oxidation  was  effected  in  the  cold 
by  the  neutral  potassium  permanganate.  The  mixture  was  acid- 
ified and  boile.d  to  complete  the  oxidation  and  to  hydrolyze 
the  nitrile  to  the  acid  group.  The  ketonic  acid  obtained 
substantiated  the  formula  originally  given  to  it  by  Forster. 


hydrolysis 


oxid.  and 


C/^C'C//3 


ZzO 


r 


t 


li 


: ‘ ■ i >.  iU  ,i  . 

1“  1 ,'3r, 


j vJ  > • 


! *-t  •,'  .' 


Oj’J  3:..:  C'.f 


T 


i-i' .•  ,^l.rij../  :ti  , '•-1  i '*  ad-  Jr' ^ j '-.'r/i'.  p« 

**5"U  Cvl  .ri  n ftu;»  ;.i,  . ,f  ..^  i‘ X . ' ?.o.  .o  :i;i.(,':  r,*  w '''K' 


i’  tt 


,!■'•  J >; 


' - - ft  i 1 1«  ^ w:»-  v 

,v  (*;  ;,•  > ! • v 

''•■•  v,"  • • ’ ■ I' . ,f  .t  i V.  (iJ 

' ' • ' '■ : ■ i .:•.•••  i.r . J''**™  . <. «;  -i.  • ••'  .■ 

t. '■ 

, -f  i • 'TO';  c'  ' (?■.;'  ' \l  iii.'i  t 0 ^ J 


\i  I Xa  t < * ' w 

. t'-  ' 

■*Xf  ;.  ' ; . ’ : n bt . .. 


3 •> 


■ , 


’■■j'  r ^ ■ r(  t»/.i 

. '■  f^HV  ' .1 


% 


j V ■ ; J J 1.  j i I i 
'j  r - 


‘ ■. 


c'JUiC^us:  ...' 


A study  of  the  preparation  of  the  anhydride  was  made  as 
the  synthesis  given  originally  was  rather  crude  and  accompanied 
by  many  side  reactions.  Peculiarly  enough,  the  anhydride  can 
not  be  produced  by  the  action  of  phosphorus  pentoxide  or  phos- 
phorus pentachloride  in  an  inert  solvent  containing  the  bromo- 
nitrocamphane , even  after  boiling  for  a long  time.  The  only 
method  seems  to  be  by  the  action  of  concentrated  sulphuric 
acid  in  the  cold.  Forster  ran  it  under  charring  conditions 
with  poor  results.  The  reaction  has  been  modified  with  ex- 
cellent results  by  dissolving  the  bromonitrocamphane  in  an  in- 
ert solvent  as  low  boiling  petroleum  ether  and  allowing  this 
to  flow  into  a well  stirred,  cool, mixture  of  the  concentrated 
sulphuric  acid  and  the  inert  solvent. 

An  attempt  was  made  to  prepare  the  Grignard  compound  with 
magnesium  of  both  the  bromonitrocamphane  and  also  the  anhydride, 
with  the  ultimate  view  in  mind  in  the  first  case  to  synthe^  ze 
ni tro- camphane  by  a new  method  and  in  the  second  case  to  open 
a path  by  which  better  evidence  could  be  obtained  as  to  the 
structure  of  the  anhydride.  But  the  halogen  in  both  cases  was 
non-reactive  in  the  experiments  and  the  original  compound  was 
recovered  unchanged.  This  behavior  was  rather  to  be  expected 
from  the  general  rule  that  the  tertiary  halogen  compounds  are 
not  very  reactive  toward s.  .magne sium  to  form  magnesium  organo- 
halides . 

The  question  as  to  the  correct  structural  formula  of  the 
anhydride  formed  by  the  action  of  concentrated  sulphuric  acid 
on  bromonitrocamphane  has  not  been  satisfactorily  settled. 
Empirically,  the  reaction  involves  simply  the  removal  of  the 


n ' , 


*r  ■ 


f ' 


'i 


'SFl 


/'  ' ' ’if  ’rii  « 

(jfjp  ‘i©'  cv^.tJ 

■«  ' -j  ' ' , II  , '•  * ' 

■'51  -^,  • 

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, ,/\^  . '»  t 

fisio  obltiJiiilRV  •fill;  , .0(U'i;»©iikjX  f) it 

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'i  -^V  ■ i'  .. 

-ftfcg'ift  i*4a  Sho'fttm  ftmm  tjjr  ni  otjf*i©4<j 

*■  -'  Vr  •'?«;  ‘'^  ■-  , r 


^ n » tiit  . iii©  I • *s  0*  u '»-  ^ rt r u<i«t  ^ -J  Xjb 


? ajtnun*:ini4  fei>v*i>t,#.fu  -/<oo  noi^P^'  'id.  ti  tJ5t%o  boHffoit 


A.  .. ' „-<. 


' f ' 5[  -j^  ^ ■ t • 

i '. '»3=o  3rtiitMio  di't  t4*ia*toi 1*16?  oiiJ  ni ’bdt>j* 

% . ‘ V 


Rm  -ni#  c ei{*t>'l  c^vrt  ti‘j i jot’ti  ©4'X  t'>^ 4'W« « t 

'*•  ' ■ ■■  o 

F '-tti  fl4*  Ai  fA j I6 


oidi  ^/TiwciXi"  l*ft«  iyiIJ’5  tu  ttpC*iiii»»q  4aZii\i4'  'd'l  tA^ 


‘*;V- 


■ ’ ■■,,.B'‘  /'.vi  ' 

^ UiiM  p lt;ii ^ 

dJ'ivr.- Pnijoc}4&iCK4  ejfX  ■,  ^ n tl^  «ii'’ 

PriJ  ct4ltt  ^wiju  't  t»ct<2  ttiW‘^4Jcd’’ to 

VS  ' 


i i*>,  ©4  ***»‘^'’  "X  i'AXf'  tijjiKiJiw  »if^  *dv  jt'» 

• • a • ; ; ■ 

(it^fi.  'j«e«n»  btu)  jBu  oi»>  nl  fcp#  v.oi^  ’^d' 


.'!■<  Ll  i.: 


•idt  aj-  r.i»  ;>a^ii4Jdv  iiiT..ca  09ft<wi:y&  T«ifX>4  4»,oii!' 

IT 


■t'  's  /I 


* tto'-*iit>  riiorO  Ofc  t/ljr  - 4.t>U  . *»t  i*\J  44  td^o.n>4oO'i4e.^ 

V *1  f ' • * '-W!'tCI  HW 't 

._•  _ . . ^ ...  . ...A* 


0^'^’  ii(w/c»  »t  s t%{lli'J-a  onS  oiu^  i L 

‘ ■ ■ ' s ■a  ‘ ■ (i  ■.’’■> 


bifid  4 «...  . qrf  t.4-  II  ifdj  4iX  0 aiA  :!£  t .:  y «fl<.d  '*  i4?  i.  • bt 'iJ.ti;  tvpd  i»*J 


t. 


itj? 


• jjtii  i;  b/^i/fig^DCtog  x-.tj^o  i"  #4  %«.»i: ; drlJ  tsh‘^^r^iii^.--p'ii9‘  «oi  t 


>-'#.•  .s. 

-•.-M'XAxt  fliultt.PnjjAtt  cJ  tit- it t.Ti2</Q*i  ■;«  ‘ t tttv  ’jcxr 

i*  b V*  * 

• ;(X  'tc  Ijf^.to'l  .oJi-  Ot  da  «<i  jJ*>oOXiK  /rtTy^  .*^^*^’*'7  '-■ 


tifl'*  otruAtiluB  b',  %i4i:5C.riair  to  nb^JO/i  \...i  t 4i:!%tXTi>x4^  , 

. , . ■'!..■■  ■ ' ;x>  •.,  " '.'  ■ ■"'  ' • ' -^-r. 

. aljr^ae  -i.' i‘i;.oxoj»tbi4  .-a  at^d  4on  «^rt  «rJ44^iS6(Mp«tlidodo'ia  4p, 

■1  ' ' ■ . ' • ' ^ •■frp,  ■ ] *.’ 

«*U  to  X<i,Vttiat'i  od4  x£m“4sf  Bttvdofttt  •4'*'  u'cIX'i^?' it i^flaST^ 

' ' ■ • ^ ^ 


£>=j:aBMa^E03e^t: 


-15- 


elements  of  water  to  form  the  anhydride,  but,  as  Forster  said, 
(4)  owing  to  the  fact  that  a nitro  group  is  involved  in  the 
dehydration,  it  is  difficult  to  ascribe  a structural  formula 
to  the  product.  From  the  fact  that  2-bromo  1-  nitro camphane 
as  shown  below  in  formula  I does  not  yield  an  anhydride,  it 
would  seem  that  both  of  the  hydrogens  on  that  carbon  atom  are 
involved  in  the  dehydration.  But  the  bromine  atom  exerts  some 
influence  because  ordinary  ni tro camphane  doe  s not  give  an 
anhydride  when  treated  with  concentrated  sulphuric  acid.  On 
first  thought,  it  would  be  expected  that  formula  ll  would  rep- 
resent the  correct  structure. 


C//, 


C/V^- 


C//-  C-CH^ 


H 


H 

cJ-  "n  £>, 


, V 


IT 


c/v 


Cl-f^ 

3l. 

/ 

1 

X 

Oy-  c'C/y^ 


Jj: 


c 


It  has  been  found  however,  that  dilute  mineral  acids  and  other 
milder  reagents  as  hydroxy lamine , alcoholic  ammonia, etc,  con- 
vert the  anhydride  to  an  isomer  which  gives  a benzoyl  deriv- 
ative. Also,  this  isomer  acts  as  though  it  was  saturated  to- 
wards bromine  and  potassium  permanganate . These  facts  with 
others  given  later,  made  it  very  desirable  to  investigate  fur- 
ther into  the  correct  structure  of  the  two  isomeric  anhydrides. 

Of  course  formula  II  is  not  the  only  formula  that  can  be 
ascribed  to  the  first  anhydride.  Very  pertinent  to  this  ques- 
tion is  the  work  of  Wallach  (15^  ”'4)  on  the  action  of  sulphuric 
acid  on  various  oximes.  He  has  shov/n  that  in  many  cases  the 
first  step  in  the  reaction  is  the  rearrangement  of  the  oxime 


1; 


'■,  ‘ " >■*■  ..  jw 

% ^1  J-  I 

f ni  .<.7t^jvnl  -a,jfc  t'A'«ix  i s iitAi  l&il  «.;l  **0  4^0  > ' 

" »■  ’■  ^ 1S^ 

Mtf4rt?^5  oJ- U<*  J Ji  . e.o 

..;  ,,,  -I  . ••*.  -V*^  ''’  '--^  ,_ 

***^  t,'j  <>■%(<  ■»5»,  *^1'  ^*  6iiJ?  * ’u  •:f«l  4^  ^ 

, Nk.  . >*  . . ..  k’*  H 


1 . 


Jfi  P4r  '•’iXwil  kr-Ah  t 


ifr? 


V 


<1^-. 


u<>^  A v i4'^  »io  <>ii4  , 

^ • -.  ;■  •,{  ' *'•■  "v ■'■ 


.’  dsi’To.-di  uvJ'fl'  »fj!jL4ii<>-V'i''viV/  /'wiS  * tirfJ  ,fti  • 


?’  '-{^  J ^ '^'  *\  * - . ‘ -■  j' 

^i.'  iTiiif  .bli>n  • Jittf fi' 


lifd 


I X 


bSiiXfW  alo^^r)\  ' Xtf  od  Uj'uw^  i I 

^ i-  • . * 4S*  •,  -I  ' '*  . •«.--  r.t  '>ji.TSf*r«  ^■im 


% <' 


i/'- 


.h:? 


‘ \ M. . «J 

i . aT 

1:.  -i 


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r i 


V ^ 


i»' 


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V.  . I 

*— •‘■ji  •) 

*^-  ...  . •• 


Si' 


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':'  ' ■ 



•’'iff 


'-^1 


t-:  . 'v  ■ ■'■■'■-Ss-  ■ ; ,;r  . ' f ;i^''^*f_ 

"*-%0.4  .«,S  J'5  . fc  JltiiiHUV;  '.iJi.  Pul  00  l4  . 4il'ia*I  4 » ’ •.•s*Ifc*4Si  'itXil'^ 

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-vitpC  /^i&.vi>i<*'i  n u**  rftiljrtr  'i‘t*rtt!L,4if(cui'  ot  <9hiih%4bifn 


- 

&ili-a‘tii4.p's4f  r >i.' i' ' Hi'  a*  it.t&R  -s  ;-iaoBi Irtf  «;'<’<* .f^  * f,. n 

BDs^  ’ ■■‘•  ‘■•.  ^ i*"  >■■ ',1 

lU’Jt’J*  8;r.d4>-!J  ' ,-^J  4;lii>| ^niMO'%4  np7i^  'v\ 

■ r-  ; ^ ^ ' '’’^t  r ; **  " ?''  ^ .X 

-’tu  «•  i <iJ  ..J  > /’t  ^ •.;  i b'  t'^  - ''?.  • '^'1 « / b tt’f  15 

. ^f>5’i‘»b'4rtr.-i»  aiioaf. nx  < ’*rid^  tr  9XirJ^ju^/*  A'^\*teii  'iU"’f<>?k| 


jfli 


b I 


Sil'  nti»  ®aV  i c.g ' ». Jlv  'ii^  ’■  'Y  ^ ‘ t >J3  .0, 

0^  anaj^ii*tvfr  ^jii7  ,k:.  ^ 

‘ il-  r.^-  'Cr^Z. 


s. '» 


t . V.: 


'iY^3 


' ■ - '■  v:y  •■■■-'■..•  ' _ ^ BV-  ■'",  ■' ••.  , ^ 


-16- 

to  the  lactam  compound  which  might  be  represented  as  follows; 

R J 

C-N-OH  ^ R 0 

R''  ^ ^^8-NH-R' 

In  other  words,  what  happens  is  that  the  oxygen  supply  from 
th  e nitrogen  atom  rearranges  on  to  the  carbon  adjacent  to  the 
nitrogen  atom  and  the  hydrogen  remains  on  the  nitrogen,  the 
lactam  being  ultimately  formed  with  one  more  member  in  the 
total  number  of  atoms  in  the  ring.  It  is  of  course  not  im- 
possible that  a slightly  similar  action  may  have  taken  place 
in  the  course  of  the  action  of  sulphuric  acid  on  bromonitro- 
camphane.  (see  next  page  for  formulas)  The  first  step  accord- 
ing to  this  mechanism  would  be  the  rearrangement  of  the  ni- 
trogen atom  into  the  ring  and  the  oxygen  atoms  from  the  nitro 
group  onto  the  adjacent  carbon.  One  carbon  is  blocked  by  the 
bromine  atom  and  the  other  carbon  has  two  hydrogens  so  we 
should  expect  the  two  oxygen  atoms  would  form  two  hydroxy 
groups,  (formula  III)  Then  , of  course,  ^he  elements  of  water 
v^ould  be  lost,  leaving  us  a ketone  group  for  that  section  of 
the  molecule.  This  is  the  mechanism  shown  graphically  in  the 
formulas.  III  and  IV.  Formula  IV  explains  more  reactions  of 
the  anhydride  than  does  II.  For  instance,  when  the  anhydride 
is  treated  with  alkali,  the  unsaturated  nitrile,  VIII  is  pro- 
duced. Probably  the  intermediate  is  the  immediate  loss  of 
hydrobromic  acid  to  form  the  temporary  trimethylene  ring 
compound  and  then  this  loses  carbon  monoxide  to  give  the  unsat- 
urated nitrile.  It  is  possible  that  Thiele's  1:4  partial 
valences  may  have  something  to  do  with  the  loss  of  carbon  mon- 


I '*■ 


Pi,  ifi  ^,^J  . o«o- 

iTjV 

, ♦ »tt.i!r-^  ■ 


*t  fitdi  rtf ’■ 

v ’^V'P:'  ■**'  W g 


''  'i'il ' 


1 


1'ift'jr.ii 


^ ■■  . . ^,,  ,„  ^ V ;i7r 

|r  ($4J-  /r  .V4k«t>i>^-  a-:-'-f-lA»!>_^iy  ..c./  4c. , 


r * '"'•CTT  ■ jJMJW  jf. 

oa’jr  •#>  '3;!'4?  jto*'  a ni^3tT«<l/fi(ii4jC>tibx<i  . *<>‘1^^' 

■ <-  \' ■ '^- ■'  ... 

, ^'  , ■*:^!^'  ’S  n V'^  ^\.  "iiMiV^^ 


ft  • '■'  > ■ ^ . j A:  • f ■ i|Wi' 

L ,,  -*  i ’'^u  i^'xtc  o *3t«  • i.  x,.(i  o^j-  it  i,  ' ^»cjrj(t  ^'0-!M»dtsi^ii:<>T4^0>4} 

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1%. f.,c  *^^-n  <wdi:'ffaii  W ♦atuoo 

' ■ :’'■>  * ■ ' .’1  I«  , : ■>  * W |:TI 

ii*,,  fldx  *J<ik  '>tt5(;,  «ff'j'  0^' 

•.J'S,  i '''-,.  ^ ' *.  •"■.  ■•-«.«- 


L^' 


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. 'M-  ' ’ %.  to'?  ' '■'  •‘•'■■^to  ^i‘Jir» 

r 'i:  / 1* I «!!-.•  ^ . Xji  » ff^A'S  . ttl \ )••  ^ ,i B<(9scii%^ 


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„ W 


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■ H‘«riv‘,  ■.  ».s /iiiV:  ♦■•' rs'i  "f.r.:<lli'''  . 'T' T.  ?fe  *s ('nlk  ,*rf  w-itf  J.,  1 w lis ■I’.^'ft vf r(/tJij«  •rf.ti®r 


v;l4’ . ainjEwi  , <:>a4)  a f%  n i .1X»  --ft 

T,  ..  ...  • .‘»t^.  ;i',-.'  •■  -’^  r.'ii.  ® ■ ■^-  k 

.4  , . " -■^;.‘  m:  . ' ?tf*  >J  I. 


fi  n ^ ' t ,1^ *1'.  .“*  i , "-"  ^ -<P  ® 


% . ■-  '■  " ' '.'-'i  , 

.'' |).v^ 


- M ,X;/"t.T  , I) I X't jb«rX'A>iyj »2; 4 ■■  '.j 


' ^1^1.  - 


V— - . N^''...'.?f  J5J,.  ■ . '^  . ' .■®'  ^ ^ 

'■  I *i}7>Mcu  «.-■>  .if^  l'a%i  SXti'J'' 


'.-..Y  » -' 

t*  '.  "i,: 

“i  I,  ' i': 


' a'"'*/*  <*■•'<* 


X.«  ii)  y*rf'  5*(»lM,iii,y o*i  J}'  ..ftXH'ir  Jii»' 

■ '. . "'■  ''””i  :to^'  :^s-^ 


vi'-;s*e*r?»>,'*sj 


' s- 


,.  ;i  * '-1^^  '^‘  g#^'*’.- ''IJ.  ‘ 

ft.  . , .« 


,,  'I 
■^SBI*  V.'  '/ 


-17- 

oxide  is  rather  remarkable  and  yet  in  another  way,  it  is  not 
so  surprising.  Consider  the  formula  IV.  It  might  be  said  to 
be  a ring  compound  of  a substituted  inner  amide.  This  same 
grouping  is  present  in  a strained  condition  in  the  intermed- 
iate, formula  VII.  It  is  a common  fact  that  amides  in  general 
lose  water  to  form  nitrides.  Perhaps  it  is  then  not  too  far 
fetched  to  say  that  a slightly  similar  reaction  takes  place 
in  this  case,  the  carbon  on  the  nitrogen  joins  with  the  oxygen 
on  the  other  carbon,  formula  VII,  and  carbon^xide  is  liberated 
to  give  the  unsaturated  nitrile. 

Forster  proposed  the  formula  IV  for  the  anhydride  but  was 
unable  to  prove  that  it  was  actually  the  correct  formula.  If 
the  ketone  group  alone  is  considered,  it  should  give  the  reg- 
ular ketone  reactions  with  such  reagents  as  hydroxylaaine , 
pheny 1-hydrazine  etc,  but  Forster  obtained  a hydroxylamino 
compound  by  treatment  of  the  anhydride  with  hydroxylamine . If 
the  ketone  were  present,  it  had  evidently  rearranged  to  the 
enol  form  and  reacted  as  such.  He  was  uhable  to  prove  that 
the  ketone  grouping  actually  existed,  although  that  seemed  the 
logical  formula  with  vrhich  to  represent  the  anhydride.  The 
main  trouble  lies  in  the  ease  with  which  the  first  anhydride 
rearranges  <vith  comparatively  weak  reagents  into  its  isomer, 
supposedly  the  enol  form  as  it  gives  a benzoyl  derivative. 

It  seemed  that  the  action  of  the  Grignard  reagent  on  the 
first  anhydride  isomer  (formula  IV  probably)  might  shed  some 
light  on  the  structure  of  the  two  isomeric  anhydrides.  Accord- 
ingly, the  anhydride  was  treated  with  the  Grignard  reagent. 


fv-  ir-- 


I ' y »▼ , , 


■'  ' ;•  '■’ll  ) »’-i‘ : ■* 


V*  ''  V i ■’‘■'‘■/'•V-'''*-  ■ ' ' '■■  ’ ■ ' -i  ■ '^-  '■■  yU^''w0'-'-  V . y^'aj 


'v^.  iil  i*<^ 


^^.f*!*  '?<■  •'■<**  ri  ''yii  i**-,  -.'/^<i ...  ' 

-'t»'*'  •';■  ' ■■  ';  ■■•‘•‘  y /.•.,;^'fa  . ■ '<y5"  '.  r,'^’  W.''  « 


VlV 


f ■'•.’• 


Ir:^|pii 


■*  H’>,l'- 

^^rL-'V-^. :'i'-!.  a; 


■>«.*  -f-  ^ 'il 


i,-.  ■.  -,  , '''T 


%e»HwrA-v-'^, 


\.-/'\i^A  , '<)»'  :*'vl!V.i  7,  . ■ ,v>'  '•”*'  li-r 

**  . - ■ *sr» 


-18- 


in  this  case,  methyl  magnesium  iodide,  and  the  comoound  formed 
decomposed  with  water  giving  a new  compound  or  derivative  of 
the  anhydride.  It  is  easily  purified  in  beautiful  crystals  and 
analysis  indicates  that  the  molecule  has  gained  the  equivalent 
of  one  molecular  weight,  ?^hich  is  to  be  expected  if  the 

ketone  group  is  present.  From  this  and  other  data  given  later, 
combined  with  the  fact  that  this  compound  yields  acyl  deriv- 
atives v/ith  acylating  agents,  such  as  acetic  anhydride,  benzoyl 
chloride,  the  structural  changes  should  be  represented  as 


So  the  correct  formula  for  the  first  anhydride  should  be  that 
as  shown  above  and  the  isomeride  probably  as  the  enol  form 
of  the  ketone. 

After  having  orepared  the  derivative  by  means  of  the  action 
of  methyl  magnesium  iodide  on  the  first  form  of  the  bromo- 

I 

ni tro camphane  anhydride,  it  was  conceived  that  it  might  be  inter-  | 
esting  to  know  the  result  of  the  action  of  alcoholic  sodium  | 

hydroxide  on  this  compound-  (formula  II)  Accordingly,  it  was  | 

treated  with  alcoholic  sodium  hydroxide  and  the  following 
changes  took  place:-  bromine  was  lost  from  the  compound,  prob- 
ably forming  sodium  bromide,  the  nitrogen  atom  was  lost  in 
the  form  of  ammonia,  which  was  detectable  by  litmus upaper  in 
the  alcoholic  vapors,  by  the  formation  of  ammonium  chloride, 
and  by  the  use  of  Nessler's  reagent.  The  product  was  an  acid 


f o Hows : 


j: 


■'  'Sf 


■ w ^ > 

' t 

■ 

^'^1.  '‘f‘  ,1—1 

fZ'  ■ 

1 ^ 

■4'  ‘ .'  //  \-.^'’'l'f.  1 

^1  * ’ ■■ 

4 ' 

i,J  • 

At-. 

^ ’ -■■■■  'Wf! 

C4^,  ^4,*J.i  „ .ty",' 

- \ r 

. »f' 

■M 


sm 


, ^.;  2 ,,, 

. >■*•  ■.  '4^;  ■>  i,^- 

%-'y 

tv  '.  t 

t. 

'it'f'*..  v%m;I^‘.  .0  41^  fyr  i'H'  . 1 ■ 

^ ' I**  m* 

./  ' s ^ » 

f^«>  ' .a, 4 


> ?. 


W\f 


T*  ‘I 


V . ^ . 4^  i A b , " ■ 


• I 


iJ  V 


. i/m 

■ *''  *'  i f ■.  . « ■ 


J ,■  'W  ..  »^J/«t-  ''Ifl 


r . , .4 


Lr:^;^ 


iC'- 


r""''  -.4  «*'iL7’ 

*'  ■ ■ * 1 4 ^ ■ %■  -^ic 

'.,'**■•  ‘i  .If  ' 


■!.f1  ,K:4l 


, j ’ • J;  » -r 

‘■'’'*  ^ t ' • ' *'i'*  ■* 
- i %’  r*-  ' , r f*'? ^ 

; • ' ,v'  . ' f 


■:'w  «• ; .•isVT'l  •-•'»■ 


t" 


*’t‘.  ■•  -•  'fi-,  jJlK '■  >.  '••  > 


*K‘ 


r^'1^UuCf.y.t:  .;:v 


!l; ' ■ ■ - > ’ " '"i 

I ft.  . A^i,.Je . . -.  :1.4-.  _ rr.'  'Z  ‘ J '•  ..Ji:/  ‘ ..^'  '.‘‘if  » 


>:  r 

't 


‘ ^ < t.<*  V 'A  '•.'».  T ^ 

• “ ^.  i A /jtf  . 1 • , ; 


' _lii' j^ .. 1'^_ jSHi-L 


^ ^ di^ ’7*^^'  *>4nwt'  ’-T  ^ '.'SW' •*  I 


'■=  \ A^^.».  %h'A-r. 


-19- 


which  gave  the  iodofora  teat  for  the  grouping  -00-CH^  and  melted 


from  67-70  degrees  C.  The  logical  compound  that  would  be  formed 
v.rhich  has  a place  here  is  the  following  methyl  ketonic  acid 
which  has  a melting  point  of  68-9  degrees  G.  The  structural 
changes  involved  could  be  represented  as  follows; 


This  furnishes  even  more  confirmatory  data  for  the  inner 
substituted  amide  formula  for  first  form  of  bromonitro camphane 
anhydride.  In  other  words,  it  completes  the  proof  for  this 
structural  formula  for  the  first  form  of  the  bromonitrocamphane 
anhydride  and  supplements  Forster's  data  for  the  isomeric  com- 
pound, the  enol  form  for  this  same  anhydride. 


■ -I'"'  , ■••i 


(v'tV 


' .V,/f 


.■  , 

jfM.  !jr^ ^ J ■ ' «i'®jj!rW.j*»'.-M^  *'*'  '•■■  '-'W.i'' *f;4^.'.‘>  ir^V-'VjM 

Pfc’-i.  » ■'  ' Z!  . : ' 1/ * - ^.T»r7  , ■ _ V- - ■ -v./itifc  :■  IF, 


[i  ‘'MC'  ■ ’,  V-  «•■'  * »•*  2;  .-,  • * . '‘47<v^..  . *ai!'  \j> 


^ ^ A; 


™'.-i  -.i  .■•'••■' iJ  ' I ' 5,%>:Sl 


-’  \vr---  .: 


^ ailrf  ••'•^^4 tiiv. '*'4?.  >' vHr.V-rta  ^^  ■;  I vfe 


4 < 


-r5 


■:  .'■^';:,,H'vfi 


I/* 


bF 


' ; ' , f t , ' ^ ' 

■'*?>  : ;.^  ■ • 


I 


ijm 


I 'j-' 


> I-  N '<v  ■ ‘if  - ‘ ^ ■;  ■'••*':>  •.  ; ■ a ■ ••  - 

,'•  .. . ■ ■ . .. ,.  i . 


■■tri 


^•■.-  -l.vr-"  ■■  ■ . '■■  <'  •;'/:/; 


; t :.-'s'^ 

' . .-  ' ^ ^ -«-■  *» 


■4  ’■■«;  VT' 


19a-  Chart  lY 


1-  Prepar 

ation 

of 

Camphoroxime . 

Material s 

• 

• 

150 

grams 

of 

camp ho  r . 

70 

g ram  s 

of 

hydroxy 1 amine 

hydro 

chi ori 

de . 

2D0 

grams 

of 

s 0 d i ua  acetate 

• 

2500 

c c . of 

95 

% alcohol. 

150  gi’ams 

of  pu 

re 

camphor  are  di 

ssol  V 

ed  in 

about  2 

500 

GC 

of  95 

alcohol  and  heated 

to  boiling  on 

the 

steam 

bath. 

200 

gra 

ms  of 

sodium  ac 

e tate 

are 

added  to  this 

hot 

soluti 

on  and 

just 

enough 

water  tha 

t the 

who 

le  forms  a horn 

ogeni 

ous  so 

lution. 

Then 

70 

grams  of 

hydrox 

ylamine  hydrochlo 

ride 

are  di 

ssolved 

in 

the 

leas 

amount  of 

wate  r 

po 

ssible  and  add 

ed  to 

the  a 

1 Coho li 

d so 

lut 

ion 

in  p 0 r t i 0 

ns  and 

th 

e whole  soluti 

on  re 

fluxed 

for  ab 

out 

two 

or 

three  day 

3 1 0 c 

omp 

lete  the  react 

ion. 

At  the  end  0 

f th 

is 

time , 

the  alcoh 

0 1 is 

di  s 

tilled  off  on 

the  s 

team  b 

ath  and 

the 

re 

sidue 

diluted  with  cold  water  to  about  5 liters  volume  v/-hich  precip- 
itates out  the  solid  camphoroxime  which  can  be  easily  filtered 
off  with  suction  and  dried.  If  the  pure  oxime  is  wanter,  it 
can  be  crystallized  out  of  ligroin,  m.p.  118  degrees  C.  Yield 


if  the 

pur 

e hydroxylamine  is  used. 

hydro 

ch  lo 

ride 

should  be  used 

yield 

of 

the  oxime  considerably. 

during 

the 

rea( 

3tion  should  contain 

Bible 

to  f 

orm  i 

1 homogeneous  sol- 

ut ion. 


2 - Preparation  of  bromoni tro camphane . 


r 


'll 


^ : 
i 

I * 


' , i ’ ’^.  'iJrJ 

-V.)' 


#- 

t A 


■ vi'7 


. . " ‘1  , C»fi-  -V 

rf-  ^ 


...9JS  ' y ■ ;':T>“'^>^  *ir 


‘ • L * ^ r j ‘ • ' o'.3lv^'* 

^’Hjj».''J|'-^*l'i':‘,  *iy^  <k^ fj4  |^‘4-ifj4.  vS 

. ‘S'  * ^ ' ' .-  ;■''  . f •.  .’  • ■ V r 'V  • '■■ft  f,K'  ''.,•  •■.< 

P.-  ''iiiif  f-n-'‘  t.tii/r  ;-'A*Vf  *,'>iii  ■ 1?  J-e«  • ii.U^  4fn^ 

^ ' « '.  vVl.  ,'a*  ',•  *L!  . ^ 


•'H 


■^■^'vV.  *'?■'  "/Wi  H ' I ^ 4C  J‘yiy  JJBW  ,J 

'■  V.  ' ' ''  %i'^sSBr  ■•  ■'' 

I ^ ^ '■’»■'  * ' ■ ■ . mV-  ’ I H- 

j jfc 


• .■•,•■-<  ''» 4 n<-.*'  : V»*  * '•  ViiJ-'t*  j,r<i  iii'i' 

:.-r.^  ■■  - ■•  ■•  n r.  •'•*.■  • ■ . ’if 


.'1 


■*'''. 

m.' 


n f. 


a : , . • c,  -V  . • . .’  J-;  '^'-WSK'S: 

, I ? ? V . ' 4 .M  ^ -H  ? 

iyi^''  liJjJ  r£tt  i9t  ^itw'Anv 


-Vi 


t 


• i?.»>  / #*/  tj4,^yi'  i>.  ;.'*v  '->  A/c^i-  *'»n’'a',,  ^r**'©  :.i‘ 


. S'.- 


'Fi  • ’•'  ^ .T3wr?.ri 

^•'^1,,  Pf->i  ■ .'•'■>*  Vi-iJ’»f^  • '#  -.,4  . ;^,  fi;  -:?:,'  '•'  i>  .ij'”»ji1'', 

[■*.,.  , ' .^-■•r'*^''  "■  ' V.  , * ’ ' ■*  ■ ■ ' ^ ’ '■'■ 

x.rM'/;  O.I..  i-.'  ■;  i<''.V«^«-’c/yi'|il»' 

■ • .'•■•  ' -V'  ■ ‘ ■ ‘ ''o  •*■'“•  ■ 'J'-.’/i#^- * ’ -M  '-  ■ .'7!*  H ' ' '" •'JSrVit** 

■■' “*■* •*'*' i1  i*Si'f‘'v ' A*. ' ijj 

, . ' " • V ’y^  .•  • •'■• ' •''•■■■■ y fy  .'■  I’SI  r . 

^ ^ ''■  { ''■'^  "-<■  ''**■  ^ w,ifov  •'*■'•  ffjy 


V '>--ilt.A>4l*  .,,/'^V^.f,.*r 


'fcl. 


-21- 

(The  method  used,  with  slight  variations,  is  almost  identical 
with  that  used  originally  by  Forster  (2)  to  prepare  the  above 
compound ) 

Mate  rials: 

600  grams  of  potassium  hydroxide  or  5'^^  of  sodium  hydroxide. 

800  grams  of  bromine. 

100  grams  of  camphoroxime . 

Pro  cedure : 

600  grams  of  potassium  hydroxide  are  dissolved  in  about 
one  liter  of  water  in  a 5 liter  r.b.  flask  fitten  up  with  a 
rapid  mechanical  stirrer  and  cooled  to  below  0 degrees  C.  Crushed 
ice  is  added  to  the  potassium  hydroxide  solution  and  a thin 
stream  of  liquid  bromine  is  allowed  to  run  in  from  a separatory 
funnel,  care  being  taken  that  no  local  heating  takes  place 
and  that  there  is  always  some  excess  ice  in  the  solution  in  the 
flask  to  insure  it  remaining  at  or  below  0 degrees  C.  As  soon 
as  the  800  grams  of  bromine  have  been  converted  to  the  potassium 
hypobromite  solution,  100  grams  of  camphoroxime  in  a finely 
powdered  state  are  added  in  email  portions  to  the  well  stirred 
liquid  containing  suspended  ice.  The  mixture  is  allowed  to 
react  under  the  influence  of  vigorous  stirring  for  several 
hours  and  at  the  end  of  this  time  sufficient  water  is  added  to 
bring  the  water  up  to  5 liters  and  the  bromonitrocamphane  is 
filtered  off  v/ith  suction  and  dfied.  When  dissolved  in  hot 
cnncentrated  alcohol  and  cooled,  the  bromonitrocamphane  crys- 
tallizes out  in  white  fern  like  crystals,  m.p.  220  degrees  C. 

The  yield  is  practically  quantitative. 


r , f 


• v'  K 


•j  ? 


I f r,<  ! ■;  ■ 


-0  V,  *' 


7 it  I h.'i» 


?• . 


' f 


' tk  •-  : 


■f.M 

^ c 


'»:  a . 1X4. 
j » t .. 


, i»  ^ I 


^ t At'  '>.‘X  4 


‘9I* 


I ■ 


V r 


TV  -*;,*.y.  jy'tjC 

■ui ' . 


• *i 


^T. 


H-  ri  ' ^ * ’ 


- / • » - 


. r.v 


. <:■  i..4iVp.( 

A ! f \xrt 

f(4ai  . 12 

>.  .’•  * ; 


I C ..  ' * 


Jrt. 


':  J 'i  i- 

i'  jti  j .j  r.  i ; -j ' 

• f S ' 1/ t>|-t 


■ i'. 

' ' * 

e * 

ii 

'if 

'1 

i 1 

'■a-fd  .^. 

1 ’,  ,'  *1X  <• 

# 

.‘i  jf  ’ 

. < t ^ ■■-• 

iii  t 

Ik 

'1 

iXrt  t: 

';l 

;> 

) 

■ hi 

...!  cftm 

r^"'' 

l! 

»!' 

1 

* 

. 'tWJ 

t ' 

ti 

\ (*■  ’■  ■-: 

- 

|«4 

t • ' - 

^.v»4 . '.p 

V * ^ 4 ' 

'•  t :'  tb  i . Jf  <•  ’1  "T  I'.r 


.X  r ‘■- 


' '■  ■'  v‘ 

o‘SAnp:i 


V L I '.n  1 ■:•  /f  * i •' n 


I 1 


% ^ 


,4 


'j  f.  •f,v  .^C-  •«  . 

x'Vt  ^'/..X-  ei<xy''i}'i  ' r.^'  tJ 

, ' '.  '■  > 

. ■ - • '-o'''  h.'.a:  , iiulV.  c-3  hi 

'..  .!  ••  7 t 


f .t 


-22- 

Remarks  : 

It  is  very  desirable  that  the  solutions  should  be  kept 
at  at  least  0 degrees  G.  to  obtain  a quantitative  yield.  It 
will  be  notic edthat  600  grams  of  bromine  were  used  instead  of 
400  grams  as  directed  originally  by  Forster  in  his  paper.  It 
has  been  found  that  use  of  the  smaller  amount  shows  a tendency 
to  the  formation  of  the  green  compound,  the  hydroxy-ni tro so 
derivative  produced  by  x-he  oxidizing  action  of  the  potassium 
hypobromite  on  the  camphoroxime . If  the  larger  quantity  is 
used,  practically  none  of  the  green  nitroso  compound  is  formed 
and  the  product  is  pure  /hite,  differing  from  the  green  com- 
pound obtained  by  Forster.  As  has  been  shovm  elsewhere  in 
this  paper,  the  ^pen  compound  is  not  the  hydrate  of  bromo“ 
ni tro camphane  nor  the  intermediate  bromonitrosocamphane  but 
is  the  compound  formed  as  a side  reaction  by  the  oxidizing 
action  of  the  potassium  hypobromi te ^ on  the  camphoroxime.  The 
same  compound  can  be  prepared  by  the  action  of  acidic  potassium 
permanganate  on  camphoroxime,  and  this  by  further  action  by 
potassium  hypobromite  does  not  yield  bromonitrocamphane,  which 
would  be  expected  if  the  green  nitroso  camphane  were  an  inter- 
mediate of  the  regular  complete  reaction.  Sodium  hypobromite 
can  also  be  used  v/ith  success,  the  same  molar  quantities  of 
sodium  hydroxide  being  used  but  of  course  different  actual 
weight  in  grams. 

Oxidation  of  bromonitrocamphane  wi th  dilute  ni t ri c acid ♦ 
Material s : 

25  grams  of  bromonitrocamphane. 


-2^- 

200  cc  of  water. 

500  cc  cone entrated  nitric  acid. 

Procedure : 

The  above  mixture  was  refluxed  in  a ground  glass  connected, 
water  cooled  reflux  apparatus  for  seven  days  and  nights  At 
the  beginning  of  the  oxidation,  much  of  the  bromonitro camphane 
condensed  in  the  cool  condenser  tube  and  at  different  intervals 
this  was  v/ashed  down  carefully  with  small  amounts  of  ether. 

After  the  oxidation  had  proceeded  for  a few  hours,  it  was  not 
necessary  to  wash  the  tube  with  ether  as  the  material  has  assumed 
an  oily  consistency  vrhich  washed  back  with  the  nitric  acid.  At 
the  end  of  the  oxidation,  the  solution  was  cooled  and  extracted 
several  times  with  ether.  The  nitric  acid  layer  was  evaporated 
down  on  the  steam  bath  until  an  oily  semi-solid  mass  remained 
which  was  then  dissolved  in  ammonium  hydroxide,  excess  ammonia 
boiled  off  and  barium  chloride  added  to  the  hot  solution,  a 
white  p re cipi tate , about  four  grams,  being  obtained  immediately 
and  more  forming  on  further  heating.  This  was  presumably  the 
barium  salt  of  camphoronic  acid  as  the  original  semi-solid  mass 
was  fairly  insoluble  in  ether.  Identification  was  not  necessary 
as  both  camphoric  acid  and  camphor  were  both  isolated  later  as 
de compo si tion  products. 

The  original  ether  extract  was  treated  with  sodium  hydroxide 
to  take  out  the  acids,  the  acids  being  liberated  by  hydrochloric 
acid,  addextracted  with  a new  portion  of  ether.  This  was  evap- 
orated almost  to  dryness  on  steam  bath,  treated  with  acetic 
anhydride  and  a drop  or  so  of  acetyl  chloride  to  convert  the 
camphoric  acid  present  to  the  anhydride.  After  heating  this 


n ■ ! ^ f T ‘V-*'  ’ ‘I 


•f'4 


f. 


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• ''-i ‘j’Tl' ■ ly'.'-^^;4‘^.i;»jS)^^  ' 0:  ■■  9.4 1 ^4,^44 

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A .tMTir  .^K,j  *'^ '■  , , ' :•  ; 


i 


-24- 


for  a short  time,  it  was  cooled,  diluted  with  water,  extracted 
ViTith  a large  volume  of  ether  to  take  out  the  free  organic  acids 
and  anhydrides,  washed  thoroughly  with  cold  sodium  carbonate 
solution  to  remove  the  free  acids  leaving  the  anhydride  in  the 
ether  layer.  The  sodium  carbonate  was  washed  out  of  the  ether 
by  water,  the  ether  solution  dried,  and  this  upon  evaporation 
almost  to. dryness  with  as  little  heat  as  possible  to  prevent 
any  hjjdrolysis  back  to  the  free  acid,  and  the  residue  dissolved 
in  hot  concentrated  alconol  gave  one  gram  of  fihe  needles,  m.p. 
220  degrees  C.  on  cooling  the  alcoholic  solution.  Mixed  m.p.,  no 
lowering.  Hydrolysis  of  the  camp-.oric  anhydride  obtained, 
changed  it  to  the  free  acid  gave  crystals  melting  slightly  lower 
that  178  degrees  0.  probably  due  to  the  ease  with  which  the  free 
acid  changes  over  into  the  camphoric  anhydride  during  the  m.p. 
dete  rmina tion. 

4-  Oxidation  of  bromonitro camphane  to  camphor . 

Materials : 

50  grams  of  bromonitrocamphane . 

200  cc.  of  water. 

500  cc  of  concentrated  nitric  acid. 

Procedure : 

In  this  experiment,  the  same  procedure  was  followed  as 
the  one  where  the  camphoric  acid  or  rather  the  anhydride  was 
isolated.  As  usual,  at  first,  the  bromonitrocamphane  con- 
densed in  the  cool  water  jacketed  condenser  tube,  which  was 
washed  down  with  ether.  After  a time,  the  bromonitrocamphane 


mrnrn : ^ 

^■\tt^r^\*^ir^4^  ,^:jtr-Ki  .wUK?  •|»vJkXJtfe  ;Uoii9s>’*,fSS.  ^ i *:c^l..ff' 

F-,  i .'■"  t V _ »w  ;■  ■ V.  ..  ,..  li.  ; ^ ' .-,  ■ ^,^*j|  -,.jr  n,; 


^ V 


ff.  fe'icr  '(HJk 

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■ V 


^ ph\i.rh\(^tiM  wi'ico.  '--Ji'' a<x4i%W 


ttW  rt«?nt'  eao'ii'i.vI»r4YtE;S« 

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f»<‘=r  ifc-rfif  ri'iOk.  o4■4^^4^4^ 

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'■  ■ ^ |||  «j|. 

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-25- 


ceased  to  condense  and  an  oil  seemed  to  return  to  the  flask 
instead.  Then  in  its  turn,  a white  solid  collected  so  much 
in  the  condenser  that  it  became  clogged.  It  was  suspected 
that  it  might  be  different  from  the  original  compound  which 
prompted  the  disconnection  of  the  condenser  tube  proper  and 
the  washing  out  of  the  solid  with  ether.  When  this  white  solid 
was  crystallized  out  of  alcohol,  it  gave  crystals  melting  at 
176  degrees  C.  the  same  as  that  of  camphor.  About  7 grams  of 
camphor  were  obtained . at tthi s step  in  the  oxidation. 

5“  Inve stigation  of  the  so-called  "hydrate ” compound . 

This  green  compound,  produced  during  the  action  of  potass- 
ium hypobromite  on  camphoroxime  was  supposed  by  Forster  (5) 
to  be  the  hydrate  of  bromoni t ro camphane . If  so,  and  if  water 
is  lost  by  drying  in  air,  then  the  ordinary  dehyrating  agents 
should  dehydrate  the  hydrate  giving  the  plain  bromoni tro can phane . 

The  action  of  cold  concentrated  sulphuric  acid  was  tried 
(by  the  same  procedure  as  given  under  the  preparation  of  the 
bromonitrocamphane  anhydride)  on  the  green  compound  and  both 
the  anhydride  of  the  plain  bromonitro camphane  and  camphor  were 
obtained  This  is  no  daubt  due  to  the  fact  that  part  of  the 
green  mixture  was  present  as  the  real  bromonitrocamphane  and 
part  as  the  nitroso  compound  as  proven  later  on  in  this  paper. 

An  ordinary  solution  of  the  green  mixture  produced  by  the 
action  of  potassium  hypobromite  gives  both  the  bromonitrocamphane 
andcamphor  on  steam  distillation. 

Warming  of  a solution  of  the  green  compound  causes  the 
color  to  turn  yellovf  and  then  this  by  distillation  with  steam 


,j.£. 


' ^;V’.  ‘ ■'  : .'  w4ksi^  •■'  ■!^'' ./  ■" ' ,r  ' 


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K '.V  ■ ■ . ’..*4  A^* 

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. mU  :••  *v  ■ ' • ♦ *.  ". 


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f. 


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r. 


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■ 'k^.  •'t  ■ iiiiSfa^  ■ '.;‘v  ' ■'  ' ■ ’ ^ f?. 

• ..t  ■ y ■•  ■ '^‘  " '^■^'^''■■'v\  m 'Viffljf  jj™  ^ 

*■;*•.."  :•> ' 'N^'  ! yppi-mf'. ^ • «»:«4i|i4i.'  ‘^4 . ’H  ' 

^r'l'-Vy;  Vvv^/' .y'  /Ckkjy.^^^ 


i-ri'f  Vt 

■ ,/^V.  ..I 


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/ Zmi?  * 


,5tiT 


-26- 

yields  camphor.  B romoni tro camphane  is  always  present  when  the 
green  compound  is  produced  by  the  action  of  potassium  hypo- 
bromite  on  the  campho roxime . 

The  green  mixture  obtained  by  the  action  jf  potassium 
hypobromite  was  also  exposed  to  the  action  of  phosphorus  pent- 
oxide  and  phosphorus  pentachloride  in  the  cold  in  inert  solvent 
of  petroleum  ether,  toluene,  benzene  etc,  both  in  hot  and  cold 
solution.  No  action  was  observed  in  the  cold  and  the  action 
on  heating  was  only  that  which  is  also  noticeable  when  the  pure 
solution  in  the  inert  solvent  is  also  heated  up.  If  the  green 
compound  was  an  ordinary  hydrate,  it  should  have  formed  the 
bromonitrocamphane  very  easily  by  these  dehydrating  agents. 


6-  Attempt  to  prepare  the  bromo-nitroso  c amphane  by  the  action 
of  bromine  on  the  camphoroxime  in  glacial  acetic  acid  and 
sodium  acetate. 

This  attempt  was  more  or  less  the  same  as  the  expetimeat 
or  attempt  of  Forster  to  prepare  alpha-bromocamphoroxime  by 
the  action  of  bromine  in  acetic  acid.  Sodium  acetate  was  used 
in  this  experiment  to  take  care  of  the  possible  halogen  acid 
liberated  but  no  action  was  observed. 

5-55  grams  of  camphoroxime  were  dissolved  in  glacial 
acetic  acid  (50  cc.)  and  about  10  grams  of  sodium  acetate  added 
and  50  grams  of  bromine  run  in  slowlyto  the  well  stirred  sol- 
ution. But  no  action  took  place  and  the  camphoroxime  was  re- 


covered unchanged 


a"  • 


V*  1 T 


L-.  •» 


i-. 


f.'  ■^  * (■!  \ 

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; 2- 


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' •'■•  '••  :«  4'Jov  : ' •••  / •' 


% T>r  i V ’ . : . i/j 


'r 


-27- 

7-  Attempt  to  synthe  si  ze  bromonitroaocampharxe  by  the  action 
of  bromine  on  camphoroxime  in  py ridjne  so lution . 

This  atte,£ipt  was  modeled  after  the  procedure  used  to  syn- 
thesizeuthe  aliphatic  bromonitroso  compounds.  (11)  6.66  grams 
of  camphoroxime  were  dissolved  in  about  20  cc.  of  pyridine  in 
a one  liter  flask  with  mechanical  stirrer,  cooled  to  a low- 
temperature  below  zero  degrees,  and  about  7 grams  of  bromine 
added  slowly  by  means  of  a dropping  funnel.  The  first  action 
was  the  addition  of  the  bromine  to  form  the  deep  bichromate 
redtcolor  of  the  pyridine  addition  compound  but  this  on  slight 
warming  decomposed  to  give  the  pyridine  and  bromine  again.  But 
the  mixture  was  v;-ithout  action  on  the  camphoroxime.  The  reaction 
mixture  should  be  characterized  by  the  deep  green  or  blue  color 
of  the  nitroso  compound  which  is  such  a valuable  test  for  the 
ketones  etc  in  the  aliphatic  series.  The  tendency  for  the 
bromine  to  add  on  to  the  double  bond  between  the  carbon  and  the 
nitrogen  is  very  small  nor  will  it  add  with  glacial  acetic  acid 
and  sodium  acetate  as  shown  elsewhere  and  also  by  Forster 
originally . 

8-  Attempt  to  prepare  the  br omonit ro socamphane . 

Materials: 

55*5  grams  of  camphoroxime. 

16  grams  of  bromine. 

40  grams  of  potassium  hydroxide  and  also  10  grams. 
Procedure: 

10  grams  of  potassium  hydroxide  were  dissolved  in  200  cc 


I'iJ- 


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-26- 

of  water  in  a one  li oer  flask, r.b.  and  about  ^00  cc  of  ether 
containing  55*5  grams  of  camphoroxime  were  added  on  top  of  the 
potassium  hydroxide  solution.  The  flask  was  fitted  up  with  a 
stirrer  and  the  mixture  was  cooled  to  about  -10  degrees  C. 
Meanwhile  a potassium  hypobromite  solution  was  prepared  by  add- 
ing 16  gramsof  bromine  to  40  grams  of  potassium  hydroxide  sol- 
ution contained  in;^  1^0  cc  of  aqueous  solution.  This  was  cooled 
to  the  same  low  temperature.  The  the  potassium  hypobromite  was 
added  slowly  to  the  mixture  in  the  flask  with  crushed  ice  to 
insure  cooling. 

The  ether  layer  was  finally  separated  at  the  end  of  the 
reaction  and  steam  passed  through  an  aqueous  solution.  Received 
27.5  grams  of  the  br omonit r o c amphane  by  distillation,  or  ^6  % 
theoretical  for  the  complete  formation  of  bromoni t ro camphane  if 
plenty  of  potassium  hypobromite  were  used.  Then  about  10  grams 
of  the  camphoroxime  were  recovered  from  the  residue  and  pre- 
sumably the  rest  was  lost  through  the  alkaline  solution  of  also 
through  the  formation  of  the  green  compound  which  has  been  proven 
clse'where  to  be  the  hydroxy-nit  ro  so  camphane.  From  this  exper- 
iment, it  would  seem  that  if  there  was  an  intermediate  bromo- 
nitroso  camphane  molecule  formed,  that  is  is  immediately  oxidized 
by  the  action  of  more  potassium  hypobromite  to  the  bromonitro- 
camphane  instead  of  more  of  the  bromonitro socamphane  being  formed 
by  the  potassium  hypobromite. 

The  quantitative  observations  in  the  next  experime.nt  show 
fairly  conclusively  that  this  is  the  case. 


-29- 


9-  Quantitative  observations  on  the  course  of  the  action  of 
potassiun  hypobromi te  on  campho roxime . 

Working  on  the  theory  that  possibly  there  might  be  an  in- 
termediate bromonitroso  compound  formed  and  that  accordingly 
there  might  be  a definite  variation  or  break  in  the  curve  of 
the  utilization  of  the  potassium  hypobromite,  the  following 
set  of  experiments  were  run  to  determine  whether  any  sharp 
variation  took  place  in  theeaction  of  the  potassium  hypobromite. 

It  might  possibly  be  that  an  immediate  addition  of  one 
mole  of  potassium  hypobromite  takes  place  and  then  a slow  oxida- 
tion of  the  bromonitroso  compound  to  the  bromonitrocamphahe  by 
the  action  of  another  mole  of  potassium  hypobromite. 

Accordingly,  exactly  6.70  grams  of  pure  camphoroxime  were 
taken  in  ether  solution,  and  put  in  with  a rapid  mechanical 
stirrer  with  10. 50  grams  of  bromine  in  200  cc  of  potassium  hy- 
droxide, the  temperature  meanwhile  being  kept  as  close  to  zero 
degrees  as  possible.  After  15  minutes  had  elapsed,  a sample 
of  2 cc  of  the  potassium  hypobromite  solution  was  removed  by 
means  of  a graduated  pipette,  diluted,  10  cc  of  potassium  io- 
dide solution  ( 100  grams  per  liter)  added,  and  then  10  cc 
of  dilute  hydrochloric  acid  to  liberatethe  hypoiodous  acid.  This 
in  turn  acted  on  the  potassium  iodide,  liberating  iodine  and 
it  was  titrated  vifith  standard  sodium  thiosulphate  solution^; 
using  starch  as  an  indicator,  to  the  end  point.  By  removing 
suitable  aliquot  parts  at  various  time  intervals  and  titrating 
the  oxidizing  -power  of  the  potassium  hypobromite  remaining;  in 
the  aqueous  solution,  the  gr%ama  of  unutilized  bromine  remaining 


:j  ‘ ‘ r.n  i-i  j ! - 0-;  .-li^  r.„' , 


■'A’f 


. .*-,  »J  '■  C.  • .*  Ui,  J ■ iu  . ■ .. 

V'  ■ 

,(  d7*i  ;ii»  ; ’ , *'t  f f ,“,f 


i n 


■ •* k;'  jpF'i  ‘ . ft.»n  '• 


in  v'lf.t:,. 


\ 


- ' i.  V . ■ . ’v  , ••  li  j’  t : cr-v  r 

\ ; i ^ f ¥ D n I • V ■*>  •.  J ; I i 


> ».  : < o 




/ 1 .' . ■ ':  I- 


' I iJ/r-  tr\: 


' r 


:-A  . 0 


■ 1 C’-L  .'T 


«4J\V 

E J :< 


' - r, hi- ^ ■ r ...  i!w'^  X - ‘ ' -- 

'■■i'O  ■ ■ '•  J r?  *7ilw  &tfn  fj !.  % . :■  ’>  • t ■-  '-y 

X-'J  -.rt  :.i'.  . i:0  VI.  •;  , 'i>s  j <,sl'  yy.yc  I'n'.o  r.yn-.^j  Ji  '-fi:-  - i Jxi-i: 

• if  ■••  i !■  V*  <.  •;  ; ’.to  , ;t  ve»r;./  !:I-,  ' *>  .,5*00  If 

. • •-  M'.;’:  ti  ;j,  •I'i^  '.  , ■!  .*  J •■f.  t v'4Jfl'  ;x*’ 5 ’:«•*'  i--4.'  • 

' » ' I. 

t . ■:  n :ij  '.  f .'  Jj'.  i.j’;  ■.■■■.'  ,.  > n, 

*.’  •* 

1 c- *)  vX’l.  _ ; c.j  ; *nc  It  .i  ■•■::;  . i".;  . V i 

' ' V ' ' 

.>r:ui:  j.v  .1  . r i' .E  j: v^Jt  ..  / ‘ ‘ 4 .t  ^ W 

•t •:; 7 •,.  ^firi  o i.l  • « ■/(-•ij  ..• 


i i 


. ' J ' 


O'it  < J*  :>  ■ *; 


r>  r .V  , 


•;  .'.  V'  ; : n f v > i ' c,-:  u;  ••  ■•-  o , 

f 1 t..; ■ 'io  C/0  t 'Jvr  :.i;  ^ . .}  > ■,  j / ■-• 

■ , '■  '7'.? VI  L ’’  '•r>o  n;f. 


< ri 


o ot>  !0  ':c 

' ; ' f 

*ic 

• ’ ( 

•.  j..- :;  I o<l  ife 


u I't,  I . 4 , V • ’"ij  -'  .(>.  '.C. i.t.,'  c I,..-  .'.1'  ■’  c 

> 

.'■f>  ur  ; ■ rtv  V u •; 'j  : : I 

t . ■ i.  : ;3..:v  r!.  ■ ; .v.  J"  .i; ; ' ? ' 


’.  c ,^i>y  S'  *.u-rr 


V *-v  1 


wOC  »,v'  n/  Trw 

'v,  I : /r  i , iiTfJ., 


/t 


V "v' 


(i?  *£• 


, •'!  f w"  - r.'  .'  J .-  -1  • ;t  i • . ‘I 1. 

f , ’ 


fi  I 0.  ■j'  t: 


■ * t ’ J f ^ J ^ J > • U i ll  - it  vi*  t« 


J ^ 

. ; Xj  . i .ir.-d  t V J j, 

..  - .0  . i;t' 

4 '.  i 

vHv 

J .1. 

I 7.  ' 

'-tr  - ’ 

■ ■'. 

' *iv  rM 

I* 


?:  ,'!P 


‘J 


-50- 


could  be  calculated.  Then  this  can  be  easily  interpreted  so 
that  ultimately  the  grams  of  bromine  used  per  unit  time  can  be 
' plotted  against  time.  The  curve  was  plotted  (see  under  theoret- 
ical) but  there  was  no  sharp  break  in  the  curve.  At  the  end 
of  two  hours  and  one-half,  the  curve  was  assiiming  an  almost 
parallel  course  with  the  axis  so  the  temperature  was  raised 
and  so  the  reaction  v/ent  to  completion.  Interpreting  the  curve, 
the  oxidation  potential  required  to  oxidize  bromonitrosocamphane 
to  bromoni tro camphane  is  less  than  the  oxidation  potential  for 
the  oxidation  of  camphoroxime  to  bromonitrosocamphane.  There- 
fore as  soon  as  any  bromoni tro so camphane  is  formed,  it  is  im- 
mediately oxidized  to  the  nitro  componnd  before  another  mole 
of  camphoroxime  is  changed  to  the  bromonitroso  compound.  These 
quantitative  results  thus  discouraged  effectively  any  further 
attempts  to  isolate  the  intermediate  bromonitrosocamphane. 

10-  Preparation  of  the  hydroxy-ni tro socamphane  by  the  action 
of  acidic  potassium  pe rmanganate  on  camphoroxime. 

This  reaction  was  first  run  by  Forster  (12)  and  the  pro- 
cedure used  here  was  essentially  the  same. 

An  attempt  was  made  to  see  if  the  green  nitroso  compound 
produced  by  the  acidic  oxidation  of  camphoroxime  by  potassium 
permanganate  could  be  converted  into  bromonitrocamphane  by 
the  action  of  potassium  hypobromite , but  it  was  found  that 
camphor  was  regenerated. 

Bromine  in  acetic  acid  and  sodium  acetate  exerted  no  effect 
on  the  hydroxy-ni tro so camphane . 


1 


. fJu.'ir.r 


- .'1.  1 


rft*'jp  ••  •.  c '.'  >s.'  - i. 


i-  f 


• ' . I 


-i  Ji-' 


C.  K* 


\ 


, .iKti.t6V'  i 

■f-  \ • 


. • r V !,> : 


w-;;.  1 


.J  * I. 


f w » '■  3 t tyj  “ 


►'  P { 


* I ‘V*, 

..  ' .^ . jAvr-Ni**. ..i: 

'■''  ' ■ 
i.  .-flL'- fe'  ..  . 

1 

. o 

' visi.  . • -. 

- - A. 

.'■•Ti  :a-:i  » 

"•  V .'?a|.*t  V.-;  0,  .' 

f'- 

^''"i 

♦,  i. 

# ‘ f f ^ ^ ^ 'V  '#\ . , 

r.i  ■- 

. > ' u :.■ 

jrwf ».  ,|,*r;o  J ^ - .'*.  ”vv'i"i  w ; i'  ••.a  -j  ^ 

J f ' ■ '■■/.'>':•.  i:..j  ' , :f  • djl?: n 

.A  uq!i*f.*  i4 

. ■'.  \ 

o.i  ‘ ' 

1 -ii  t c'.-' i ■'  <.■:!  •',  ■)w’' 

LU-. 

■ - J 


«9v* 


..  N J,i»6  ‘■'5|l  fif;?" 

■ I ' ' ''•'  •’  ■ '■  i ■ ^ 

• * .-m*'  • I 


'V.Ot  fc 


.lai 


t 


) . I > 


1 


-51- 

From  the  above  data,  it  appears  that  the  green  compound 
is  neither  the  hydrated  nitro  compound  nor  the  intermediate 
bromonitroao  compound  but  purely  a side  reaction  from  the  main 
route . 

1 1"  Action  of  potassium  fe rri cyanide  on  oamphoroxime  in  alkaline 
solution* 

505  grams  of  oamphoroxime  were  dissolved  in  about  ^0  cc 
of  concentrated  potassium  hydroxide,  cooled  to  about  0 degrees, 
and  an  aqueous  solution  of  potassium  ferricyanide  (15*2  grams) 
added  drop  by  drop  by  means  of  a dropping  funnel.  Almost  im- 
mediately, a white  flocculent  precipitate  began  to  form  which 
turned  to  a bluish  green  color  The  rea.ction  was  allowed  to 
proceed  for  about  one-half  an  hour  when  it  was  diluted  to  one 
liter  with  distilled  water  and  the  bluish  green  compound  fil- 
tered off  by  suction.  Dfied  on  a filter  plaice,  it  gives  the 
same  unstable  hydroxy-ni tro so  compound  in  almost  quantitative 
yields  as  prepared  originally  by  Forster  by  the  acidic  oxida- 
tion with  potassium  permanganate.  However,  this  is  a much 
better  method  for  the  preparation  than  by  the  oxidation  with 
acidic  permanganate. 

12-  Control  of  reaction  with  potassium  hypobromi te  to  produce 
the  hydroxy-nit ro so camphane  as  the  main  product. 

The  conditions  of  the  reaction  of  the  >potas sium  hypobromite 
on  the  oamphoroxime  can  be  so  varied  so  as  to  give  pure  bromo- 
ni tro camphane  or  to  give  primarily  the  hydroxy-aitrosocamphane. 


, ^jjn  

wC  <fl.  '•  t.-i  f '<  C'I-.::?V  ' ■■  ■ .'n  •:'  ■•'■/' 

"T"  ' .Qs' 

- ' - ' ' . • - ■ ' ' 

'*■  • ■ •'  •,  'V  t f ( !<■  ;.  . "p  ,i V j -V  - ,!/ J <*  n , fii- ■ ■> . ' , ^ iie 

. I . r.  w ^ ^ .•;  .-i  ..  v v 

^ •'  -»  •■  1-:  I'jn-lc  Mv  , , ){ f u' i 

V. «»  ■ ' » I i . ■ ‘ .0*;  ^ i,  J .,  I.  .1  'I  t,  ' : 'j  .‘*1'  I'k.-'’  ~i  r -i  d 3 .' 

''  ' ' ' * 'f  -ll  ' 't  ' ■ . J .',  :,'i  , ; . tj  i ' ' ': 

• ■ ’ ■'<■.  ' ' i . . ■ ^ ' n*.  - ’ “ ; . g^j  ‘ :,;i 

.■*  . ‘ ' • ' » 


rSf;  ; r.  c,  ..  :,i. 

l»V,i  T'  ■ c ' i./  ' “k  ■ :t  ^ V'J  ^ " v'  ; 


. v'  ; 

0.  . i , ■’■  •.  •>  ■ •».*'  ''-ir.  ■ ' ,1  \ 'i  ■ 


- :i‘Vr  ^ 

1 ■'■  *1!»  J O u/jr 


;<1  :-i  V (ij  fi'  ! V '.•'t  .1-';;  , _ •■',7  ,()  ,,  , >• 

. >■'.  -mr  ' 


k., ' <1- 


' • •’:  C ■■'■  V {■  ■)■  f * /•. ' • i J’  £i ' 

■'i  c ' w «»; •-^••. .' »•  i>  '.I  r,-  litff.  t’3  :;  - S 


*-♦  , ):  < 


- '•■  ‘ ■ ■>  '■■■  Jr  : 'io  ' ;>  ikit 

;LJ6 


^ :•  c ■)  0 3 . : ' **  ^ ^ ^ ^ '1  ’ -•  ■ C'  i ' . 1,6 


■ 'r. 


•;  J :r  ■■ 

/ 

J 


-52- 

For  the  preparation  of  the  pure  bromonitrocamphane  with  practic- 
ally none  of  the  hydro;cy-ni t ro so camphane , an  excess  of  bromine 
and  addition  of  the  dry  powdered  camphoroxime  is  essential  as 
described  in  detail  elsewhere  in  this  paper. 

For  the  production  mainly  of  the  hydroxy-nitroeocamphane, 
by  the  use  of  potassium  hypobromite,  take  the  following  pro- 
cedure:- Take  5*55  grams  of  camphoroxime  in  about  ^00  cc  of 
ether  over  200  cc  of  aqueous  solution  containing  40  grams  of 
potassium  hydroxide  and  added  the  bromine  slowly  to  this  well 
cooled  solution.  The  ether  so lution  immediately  begins  to  take 
on  the  emerald  green  color  characteristic  of  the  hydroxy-nitroso- 
camphane.  Some  of  the  bromonitrocamphane  is  of  course  produced, 
but  this  modification  above  has  a tendency  to  cause  the  oxidation 
effect  of  the  potassium  hypobromite  to  predominate  and  assert 
itself  immediately  on  the  camphoroxime. 

15-  Oxidation  of  inf ra- campholenOni tri le  by  the  action  of 
potassium  permanganate . 

About  20  grams  of  the  inf racampholenenitrile  were  taken 
and  placed  in  a one  liter  flask  equipped  with  a mechanical 
stirrer  with  about  600  cc.  of  water  and  ^00  cc.  of  a ^ % solu- 
ition  of  potassium  permanganate  run  in  slowly.  The  flask  was 
kept  cool  for  the  first  part  of  the  reaction  in  order  to  cause 
the  production  as  far  as  possible  of  the  di-hyd^xy  compound 
of  the  nitrile.  Acid  oxidation  at  this  point  can  not  be  used 
as  strong  mineral  acids  cause  the  rearrangement  of  the  double 
bond  down  to  the  corresponding  a Ipha-campholytic  nitrile. 


1 -.i' 


j 1: 1 ,.i  -/ r 

I ' -'■*  v ‘ ^ 


.:  I'  ■-  J ?.  f* . 


A4 


* > i-  ®!r  - * • ■ 


I*  M. 


.(;  ‘.!0  >:i- 


r o • ^ ^ 


'i  i.  -.  .i  ; J 


i .•  '/!'  -.:  *..  .•  CA-'Ce.  «!...■ 

■'^  ■ ' 

- ’ ( '^ 

. j ^ i,  .'  ica^Ti ; 4 V,  • '*.  ' 

■ 'fiVf  ; ".ire 

5 ■,■ --5  0 

At  flic.  [';.' 

.7lA,V'  ’ ■•*-.o.;Sv..  'ic.-V.  • 

, "■*  -’.A  l-.«j  'J  ‘ u 'j  h i >;  viil  (-1^  . 

, -V.  ■.  A 

i • >3.^^  w"i 

, ’■  • T ■•■,.* 

V ; ■ :.  'fu.'j'  .5  4:  ,.  . 

ii 

li 


- • * f -f  ‘ ■ ' >,  , .».• 

♦ J ...  - ^ V ' '.  M,  ^ ■ 

t C T ' 'i'  'l:  ,1  X'  ; jvri"  ' ft 

■ 4i  ->■'.  c ...  ' J ■,  • ’■•r- .« -*■ 

- 1.-^  i .;...■;  -V-  .V  i'  - . 


• ::  ^ ...  '4 


v‘  ; 


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, V ' , '■  ■■  '■'■  ■ 


a?..*';.;' '^wJ : 


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*T^ 


,iU 


r . .'v 


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'xt.< ' at ',  -^1 


^.-.x  " N.  fJV-' ■ . iT 

mt*.  ,f) 


i ;;•  >^.a  ft ('■  %. !?-■'.'  t ;,■  ••; ■ ’ ‘i v -s su <.» ;, ^ . C*. ■ v ^ ' o *f. A 


71: 


i i:-  ....;•  a £>iytv  : ..  y •.? 

. *r'>, 
■ 1 

iVf  i:-i' 

V ■ -V.' 

■■•'  -V  . - ♦'♦'  •’'>/■; ‘*■<•4  4 

1 . ',' 

'v'  ,'j'k 

.'I;.:,  "(.■.;!•  'lJ:Z 

- ' ■'  '*  - ■ 

•‘  - ‘ •'  ''-.'I 

.jUsiLi  . . Y,.r  nl  nm 

• 'i.i 

•'  ■ » 

i til' 

'1  ro»3A''4t|o 

„,  .'  ’ >■ 

-P  A'A-- ,'■  •.;■  .•,c'r:4  -i't  . rKiJt  'Jc  t 

* .••  .;  . 

t 

^••i:  V C’XJ  ; •.;  : l>\ 


it 


:4 


1j  . : . ’ . ' ::!■„  •■  jM;  It' 


'■  ■'•'*'  ^ ^ rnt"  .>  ii 

'•  •’  • RlWI?6WlBl 


i 

4 

1 


V i 


y.  > , .V  .*  ■’"•‘'v . •■> v.i3j<T-l.s  ■ A 7 ^ •''i-  a ■ - ,^»  -C'J  ..< 


'All] 


Vfo' 


-55- 


Consequently , alkaline  oxidation  was  used  to  obtain  the  di-  hy- 
droxy compound  and  then  the  solution  was  made  acid  and  oxidi- 
zed further  by  the  vigorous  acid  oxidation  for  several  hours. 

The  excess  of  the  oxidizing  agent,  mainly  the  manganese  dioxide, 
was  decomposed  by  the  addition  of  sodium  sulfite  and  the  cold 
solution  extracted  several  times  with  ether,  the  ether  layer 
then  being  put  in  flask  with  condenser  and  hydrolyzed  with 
strong  alkali  for  several  days  to  hydrolyze  the  nitrile  to  the 
acid.  At  the  end  of  this  time,  the  reaction  mixture  was  acidi- 
fied with  acid,  extracted  several  times  with  ether,  the  ether 
extract  treated  with  alkali  to  take  out  the  acids  formed,  in- 
cluding the  ketonic  acid  wished,  the  non-acid  portion  being 
removed  by  the  ether  from  the  alkali.  Then  the  acids  were  lib- 
erated from  the  ether  by  acid,  extracted  several  times  from 
the  cold  aqueous  solution  (as  the  ketonic  acid  is  somewhat 
soluble  in  water)  with  ether,  the  ether  evaporated  almost  to 
dryness  and  a small  amount  of  water  added  which  was  then  heated 
to  boiling  On  allowing  the  aqueous  solution  to  cool  slowly 
over  night,  there  crystallized  out  a very  small  amount  of  long 
needle  like  crystals  on  the  side  of  the  test  tube.  These  were 
transferred  to  a melting  point  tube  and  they  began  to  melt  or 
soften  at  107  degrees,  finishing  melting  at  110  degrees  C. 
(Melting  point  of  the  ketonic  is  109-11  degrees  C)  The 

slight  lowering  is  probably  due  to  a slight  impurity  in  the 
crystal s . 


f 

s 


I 


l4-  Preparation  of  bromoni t ro camphane  anhydride . 


-^4- 

Materials : 

1 liter  of  concentrated  sulphuric  acid. 

400  cc.  of  petroleum  ether,  b-p.  25-40  degrees  best. 

100  grams  of  bromoni t ro camphane , 

Procedure; 

One  liter  of  concentrated  sulphuric  acid  was  put  in  a 5 j 

liter  r.b.  pyrex  flask  which  was  connected  up  to  a mechanical  J 

stirrer.  This  v^^as  surrounded  with  an  ice  and  salt  mixture  and  | 

i 

about  100  cc.  of  the  petroleum  ether  added  to  the  sulphuric  acid. 
While  the  sulphuric  acid  mixture  was  cooling  down  to  -10  degs.  C., 
100  grams  of  pure  bromonitro camphane  were  dissolved  in  about 
500  cc  of  petroleum  ether  (same  as  above).  This  was  placed  in 
a separatory  funnel  and  allowed  to  drop  slowly  into  the  cool 
mixture  of  the  sulphuric  acid  and  petroleum  ether.  The  sulphuric 
acid  turned  slightly  yellow,  then  from  orange  to  deep  red  but 
did  not  turn  brown  or  black,  as  observed  by  Forster  in  his  sim- 
ilar method.  Nor  were  any  decomposition  products  observed  when 
this  method  was  run  carefully.  After  a short  time,  usually 
about  one-half  hour,  the  stirrer  was  removedf^he  petroleum 
ether  rises  to  the  top  in  a layer.  This  contains  some  of  the 
bromoni tro camphane  anhydride  but  most  of  the  anhydride  is  in 
the  sulphuric  acid  layer.  The  two  layers  should  be  separated 
here  at  this  point,  and  the  sulphuric  acid  poured  yith  stirring 
onto  finely  crushed  ice  which  precipitates  a flocculent  white 
solid.  This  is  either  filtered  off  after  dilution  v/ith  water, 
or  it  can  be  dissolved  and  extracted  out  with  ether.  It  is 
the  washed  .ith  sodium  carbonate  solution  to  remove  the  last 


t-  <r;- 


r" 


■' 


-'■il 
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i 

I 


. ; o«i!  .,/  ’■  , >;  t-vtt' 

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. / 


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Ki  f ■.,'(.  a ‘ ,•  L*:\t  ,"■  •■  ^ i-.l  . ■,  / . 1.  ',  II.  .f itj"’ 

*'  A''(  ■•,  ^ ' ..  ‘ 

»-i  3i  ■ ,i:  *0  •,.  . ‘i  .*{.•'  0 ;.''..'pf'..  ;• 


' i 


■>: 


' .J  ' , '-  I.'  r .•'  t,'  ,*>  : 

;•  »-  ■ ;•  J ' j'i.  i ■ ••  '■  • r 

. ' " .J  J ^ ^ U V '.J  t'.-  /‘X  *!'  ■-’.  iii.j  ,' 


.:  .'X 


• N ' tu'i 

'*  ^ ■'  • ■ '*  ' <■■'  i-'- 

• /f  ''^ 

• •'•  ..'  *>  ,r'.  ,«i;r-  ‘ bfti-d 


•;  c ..r  r..  t'.  X : i/  ’ I,.' 

. ^ 


V 1.  i>H 

X -v^;  ' * *•  V 

V"*  \ •- 

■;  ^%-ff  V 

: 1.'  !.  ■' 

i: 

, 

■:.  i>4v  >■ 

. . ..■'"  ' ',  'I  H .. 

c t 

. ■ v , . {':  V f 

' ' c i: 

' I'C  V 1..  1,  ’ ' 

(.'4.  iiJ 

-55- 

traces  of  the  acid,  washed  again  with  water,  and  the  ether 
removed  Ly  evaporation  on  the  steam  bath.  The  residue  can  then 
be  crystallized  from  concentrated  hot  alcohol  to  give  an  almost 
quantitative  (70-  100  % yields)  of  the  bromoni tro camphane 

anhydride , 

Remark  s : 

Forster  in  his  paper  used  almost  the  same  method  except 
that  he  added  his  bromonitrocamphane  compound  directly  to  the 
concentrated  sulphuric  acid  with  the  result  that  he  caused 
considerable  local  heating  with  charring  and  under  these  charr- 
ing conditions,  a lot  of  undesirable  by-products  were  formed. 

By  the  use  of  the  above  method  that  I have  described, athe  de- 
hydrating action  is  toned  down,  so  to  speak,  so  that  the  heat 
produced  can  be  controlled  and  the  dec ompo si tion  products  are 
eliminated  entirely  and  the  product  obtained  is  almost  pure 
■white  without  recrystallization.  When  the  petrol  ether  solu- 
tion of  the  bromoni tro camphane  is  added  to  the  mixture  of  the 
sulphuric  acid  and  pure  petrol  ether,  it  seems  that  the  bro'mo- 
ni tro camphane  is  almost  immediately  taken  over  into  the  sul- 
phuric acid  and  dehydrated  at  once.  Considerable  heat  is 
produced  by  the  action  of  the  sulphuric  acid  on  the  bromonitro- 
camphane but  this  is  compensated  for  by  the  ice  and  salt  bath 
aided  by  very  vigorous  stirring  so  that  the  temperature  never 
rises  above  -5  degs  0.  Any  greater  rise  of  temperature  during 
the  addition  of  the  petroleum  ether  solution  of  the  bromonitro- 
camphane decreases  the  yield  of  the  anhydride. 

The  main  point  about  this  modification  of  Forster's  method 
is  that  it  enables  the  operator  to  keep  the  reaction  'well  in 


I . • '•.  ’ / • .- 


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'.4^'  ■•?■  ■ '■  :■■  s,V  ■>,!•  > i'1  ' ’r'.  J.',; 

-■  ' ■" " .■’.  ■ t/  I T.  ‘'i  . 

• •'  *•  J 4 * \\i'0  fn. 

' : • >•  ' 7 

” '■  a"  i J jri' I j t i.  • j;  ‘ j ' j j_'  . / 

i*  lu  »."<>•*  ••  4 • 

■'  rSi’Cl..  '.  ■' 


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"V  A 


-56- 


hand  and  prevents  local  heating  effects  and  subsequent  decomp- 
osition. 


^5“  Attempt  to  prepare  the  organo -magnesium  c ompounds  £f  the 
bromonitrocamphane  and  als  o ^he  bromoni tro camphane  anhydride . 

The  attempt  to  prepare  the  magnesium  halide  compound  of 
bromonitrocamphane  was  mainly  in  hopes  that  it  would  furnish 
a better  method  for  the  preparation  of  ni tro camphane . The 
regular  procedure  for  the  preparation  of  Grignard  reagent  was 
used,  suspension  of  magnesium  in  ether  with  the  halide  compound 
and  addition  of  some  iodine  as  a catalyst  for  the  reaction. 

But  the  bromoni tro camphane  would  not  react  under  any  of  the 
conditions  tried  even  under  long  refluxing  and  also  after  the 
addition  of  a small  amount  of  methyl  iodide.  The  original 
compound  was  recovered  unchanged  The  non- reac ti vi ty  of  the 
halogen  was  more  or  less  to  be  expected  since  it  is  a tertiary 
halogen  and  the  tertiary  halogen  compounds  in  general  react 
with  difficulty  with  magnesium. 

The  same  regular  procedure  was  tried  with  the  first  form 
of  the  bromoni tr o camphane  anhydride  and  the  same  results  were 
obtained,  the  halogen  being  also  non-reactive  in  this  compound. 
The  idea  here  was  to  furnish  some  means  by  which  the  true 
structure  of  the  anhydride  compound  could  be  more  clearly  eluc- 
idated. 


16-  Action  of  the  Grignard  re  agent  on  the  bromoni tro  camphane 
anhydride . Methyl? magne sium  iodide  being  used . 


I 


-57- 


Matorial 8 : 

10  grams  of  broraoni t ro c amphane  anhydride. 

20  grams  of  methyl  iodide. 

5 grams  of  magnesium  turnings. 

250  cc  of  dry  ether. 

Procedure : 

5 ^rams  of  magnesium  turnings  are  immersed  under  200  cc 
of  dry  ether  in  a one  liter  flaslc  connected  to  a reflux  con- 
denser with  air  tight  connections.  A small  amount  of  iodine 
is  added  as  a catalyst  to  the  flask  and  20  grams  of  methyl  io- 
dide added  in  portions  so  that  the  vigorous  reation  is  well 
under  control  until  all  is  added.  The  solution  is  refluxed 
until  all  action  has  ceased  and  ??hen  there  is  only  a very  small 
amount  of  magnesium  left  in  the  bottom  of  the  flask.  Then  10 
grams  of  the  bromoni t ro camphane  anhydride  are  dissolved  in 
about  50  cc*  of  dry  ether  and  added  in  small  portions  through 
the  top  of  the  condenser  and  this  mixture  refluxed  for  several 
hours  'vhen  the  flask  is  disconnected,  and  small  amounts  of  water 
added  cautiously  to  decompose  the  Grignard  compound.  Then  after 
the  main  reaction  has  ceased,  some  dilute  sulphuric  acid  is 
added.  The  whole  is  stirred  well,  at  least  for  several  Minutes 
and  the  ether  separated  off  by  means  of  a separatory  funnel, 
washed  with  water,  sodium  carbonate,  again  with  water  several 
times,  dried  over  calcium  chloride  and  evaporated  down  almost 
to  dryness  over  the  steam  bath.  At  this  point,  if  the  liquid 
residue  is  allowed  to  cool  slowly  so  that  the  last  portion  of 
the  ether  evaporates  off  spontaneously,  the  derivative  crystall- 
izes out  in  large  lustrous  transparent  places, m. p« 1 17-8  degs.C. 


-58- 

It  is  insoluble  in  acids,  and  alkalies,  soluble  in  ether  and 
alcohol  but  insoluble  in  water.  It  isconveried  readily  into 
the  Co r re  spending  acyl  derivatives.  Analysis  of  the  compound 
formed  by  the  action  of  methyl  magnesium  iodide  on  bromonitro- 
camphane  anhydride; 

• 1705  gas.  gave  .12^0  gms.  AgBr  or  .0524  gms  bromine. 

Found  for  the  % Br  50*75  % 

Theory,  G^iHlSONBr  50.75% 

By  treating  the  above  compound  with  benzoyl  chloride  and  sodium 
hydroxide  according  to  the  Scho tten-Baumann  reaction,  a benzoyl 
derivative  is  obtained  fine  crystals  out  of  the  hot  dilute 
alcohol,  m.p.  115-4  degs  0.  It  will  also  crystallize  from  ether 
in  star  shaped  needle  colonies.  Analysis  of  this  benzoyl 
derivative  of  the  first  compound  gave; 

.2l4l  gms  gave  .10^4  gms  AgBr  or  21.75  % Bromine. 

Theory  for  the  tompound  CijqH2202^®^  21. 90  % Bromine. 

17-  Action  of  alcoholic  sodium  hydroxide  on  the  compound  pro- 
duced the  Gr ignard  reaction  (seel6). 

To  observe  the  action  of  alcoholic  sodium  hydroxide  on 
ohe  compound  produced  by  the  action  of  methyl  magnesium  iodide 
on  bromoni t ro camphane  anhydride,  about  5 grams  of  this  derivr 
ative  were  dissolved  in  about  25  cc.  of  ethyl  alcohol  and 
10  cc.  of  concentrated  sodium  hydroxide  added  and  the  mixture 
or  solution  boiled  for  a few  minutes.  A strip  of  red  litmus 
wetted  and  suspended  in  the  vapors  issuing  from  ohe  flask  was 
turned  red,  while  clouds  of  ammonium  chloride  were  produced 
when  an  hydrochloric  acid  bottle  was  brought  in  proximity,  and 


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-59- 

the  vapors  turned  a portion  of  Nessler's  solution  a deep  car- 
mine red,  all  showing  the  loss  of  ammonia.  The  alcohol  is 
boiled  off,  the  residue  taken  up  in  ether  and  water  together, 
acidified  with  acid,  extracted  with  ether,  the  acids  extracted 
from  the  ether  with  sodium  hydroxide  and  the  acids  again  lib- 
erated from  the  alkali  by  acid  and  removed  to  the  ether  layer. 
This  v/as  evaporated  spontaneously  the  rest  of  the  way,  whereby 
slight  yellowish  crusts  separated  out,  which  are  soluble  in 
alkali, but  insoluble  in  water.  A sample  of  Lhese  crusts  when 
tested  according  to  the  iodoform  reaction  gave  a heavy  precip- 
itate of  iodoform.  Melting  point  gave  67-70  degrees  C.  The 
wide  range  of  the  temperature  was  probably  due  to  slight  im- 
purities as  the  quantity  was  too  small  to  purify  as  much  as 
desired.  The  compound  gave  negative  qualitative  tests  for 
halogen  and  nitrogen,  It  was  undoubtedly  the  methyl  ketonic 
acid  that  would  be  expected  if  the  structures  of  the  preceding 
compounds  were  as  supposed. 


T 

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“^>4=:  '.■■w-*'^!  t 'jfiJtftjr  n ?.J ! a ''vifl^' 

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XX  ... 

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-40- 

V- SUMMARY. 

1-  Broraoni t ro camphane  on  oxidation  with  nitric  acid 
breaks  down  successively  into  camphor,  camphoric  acid,  and 
camphoronic  acid. 

2-  The  course  of  the  action  of  potassium  hypobromite 

on  camphoroxime  has  been  found  to  be  brominatlon  of  camphor- 
oxime  and  then  oxidation  to  the  bromonitrocamphane . No 
bromonitrocamphane  hydrate  is  formed  as  was  supposed  by 
Forster. 

5“  Potassium  hypobromite  may  also  act  as  an  oxidizing 
agent  on  camphoroxime  to  produce  hydroxy-nitroso-camphane , 

4-  Strenuous  permanganate  oxidation  of  inf ra-campho- 
lenenitrile  and  hydrolysis  ultimately  yields  the  correspond- 
ing ketonic  acid. 

5-  Bromonitrocamphane  anhydride  has  been  prepared  by 

an  improved  method  and  the  structure  of  the  anhydride  eluci- 
dated by  its  behavior  with  the  Grignard  reagent,  methyl 
magnesium  iodide.  Since  the  structure  of  the  anhydride  is 
now  an  established  fact,  a logical  explanation  is  provided 
for  the  unexpected  transition  from  bromoni trocamphane  to 
inf  ra- c ampholenenitrile . 


, ,, 

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-41- 


VI-BIBLIOGRAPHY. 


. (0 

Forster, 

Trans.  Ohem. 

So  c . 

(1397)  11, 

1050. 

(2) 

It 

II  It 

It 

11* 

1 i4i , 

( 1399) . 

(^) 

n 

It  II  II 

n 

u> 

251, 

(1900). 

(4) 

n 

II  11 

It 

655, 

( 1901) . 

(5) 

n 

It  n 

» 

I2» 

108, 

(1901). 

(6) 

II 

II  n 

II 

12. 

644, 

(1901). 

(7) 

II 

II  II 

II 

12. 

264, 

( 1901). 

(6) 

II 

II  II 

It 

12. 

1005, 

(1901). 

(9) 

II 

II  II 

II 

865, 

(1902). 

(10) 

Gwinn.,  Thesis,  University 

of 

111.  (1920). 

(11) 

Piloty , 

Ber.  d.  Deut 

. Ch. 

5099, 

( 1902) . 

(12) 

Forster, 

Trans.  Chem 

. So  c 

11 

, 199, 

( 1897). 

(1^) 

Wal lach . 

Anna  lien. 

122. 

1 

( 1899) . 

(14) 

Wal lach . 

Annallen, 

112. 

171, 

( 1900) . 

Forster, 

Proc.  Chem 

So c . 

28> 

515, 

(1912). 

Forster, 

Tians.  Chem 

Soc . 

11. 

78  , 

( 1905). 

Pope , 

It  II 

^71, 

(1895). 

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n It 

11 

11. 

987, 

(I9OI). 

Armstrong,  Lowry.  Proc  " 

11. 

162, 

(1901). 

Kachler 

& Spitzer  Proc , ” 

11. 

217, 

(1901). 

-42- 


yil-  VITA. 

The  author  was  born  on  the  7th  day  of  April,  1897# 

Columbia,  Missouri.  he  attended  several  grade  schools,  finish- 
ing the  eighth  grade  at  Macomb,  Illinois.  Then  he  entered 
the  Western  Illinois  State  Teachers'  College  Academy  and  grad- 
uated from  there  at  the  end  of  four  years,  1911~15*  In  the  fall 
of  the  same  year,  he  entered  the  University  of  Illinois  in 
the  regular  chemistry  course  and  graduated  with  the  B.  S.  de- 
gree in  June,  1919*  Graduate  work  was  begun  in  the  same  Uni- 
versity and  the  M.  S.  degree  received  in  June,  1920.  From 
that  time  to  the  present,  the  author  has  been  doing  further 
graduate  work  here. 

The  writer  taught  quantitative  chemistry  as  Graduate 
Assistant  during  the  year,  1920-21,  in  the  University  of 
II linoi s . 

Publications:-  "Syntheses  of  Chromanes  and  Coumaranes"  j 

Journal  of  the  American  Chem.  Soc.  Vol.  42,  157#  (1920) 
by  R.  E.  Rindfusz,  P.  M.  Ginnings,  V.  L.  Harnack. 

Fraternities  and  Societies:-  Gamma  Pi  Upsilon,  Phi 
Lambda  Upsilon,  and  Associate  Member  of  Sigma  Xi. 


